WO2014112683A1 - Conductive ink composition and method for forming electrode using the same - Google Patents
Conductive ink composition and method for forming electrode using the same Download PDFInfo
- Publication number
- WO2014112683A1 WO2014112683A1 PCT/KR2013/001997 KR2013001997W WO2014112683A1 WO 2014112683 A1 WO2014112683 A1 WO 2014112683A1 KR 2013001997 W KR2013001997 W KR 2013001997W WO 2014112683 A1 WO2014112683 A1 WO 2014112683A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particles
- ink composition
- conductive ink
- electrode
- copper
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000010304 firing Methods 0.000 claims abstract description 25
- 238000007650 screen-printing Methods 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims description 132
- 239000002245 particle Substances 0.000 claims description 108
- 229910052802 copper Inorganic materials 0.000 claims description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 63
- 239000002923 metal particle Substances 0.000 claims description 61
- 229910052709 silver Inorganic materials 0.000 claims description 45
- 239000004332 silver Substances 0.000 claims description 45
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 44
- 239000003960 organic solvent Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- -1 triazole compounds Chemical class 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 230000009974 thixotropic effect Effects 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 230000004907 flux Effects 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 6
- 239000004210 ether based solvent Substances 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- 239000012756 surface treatment agent Substances 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 229920000180 alkyd Polymers 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 239000005456 alcohol based solvent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 3
- 150000004292 cyclic ethers Chemical class 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- CYKDLUMZOVATFT-UHFFFAOYSA-N ethenyl acetate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=O)OC=C CYKDLUMZOVATFT-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000005453 ketone based solvent Substances 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- IGODOXYLBBXFDW-UHFFFAOYSA-N alpha-Terpinyl acetate Chemical compound CC(=O)OC(C)(C)C1CCC(C)=CC1 IGODOXYLBBXFDW-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 44
- 238000002156 mixing Methods 0.000 description 10
- 238000000206 photolithography Methods 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 7
- 239000004642 Polyimide Substances 0.000 description 6
- 230000005496 eutectics Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 229940043232 butyl acetate Drugs 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000010199 sorbic acid Nutrition 0.000 description 2
- 229940075582 sorbic acid Drugs 0.000 description 2
- 239000004334 sorbic acid Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- RGTIBVZDHOMOKC-UHFFFAOYSA-N stearolic acid Chemical compound CCCCCCCCC#CCCCCCCCC(O)=O RGTIBVZDHOMOKC-UHFFFAOYSA-N 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- 239000001169 1-methyl-4-propan-2-ylcyclohexa-1,4-diene Substances 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000005973 Carvone Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 101001045744 Sus scrofa Hepatocyte nuclear factor 1-beta Proteins 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 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
- 238000007792 addition Methods 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- KJDZDTDNIULJBE-QXMHVHEDSA-N cetoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCCCC(O)=O KJDZDTDNIULJBE-QXMHVHEDSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007823 ocimene derivatives Chemical class 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- UQXWTFXBTIZNGU-UHFFFAOYSA-M oxygen(2-) zirconium(3+) chloride Chemical compound [O-2].[Zr+3].[Cl-] UQXWTFXBTIZNGU-UHFFFAOYSA-M 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000007875 phellandrene derivatives Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- DPUOLQHDNGRHBS-MDZDMXLPSA-N trans-Brassidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-MDZDMXLPSA-N 0.000 description 1
- XJPBRODHZKDRCB-UHFFFAOYSA-N trans-alpha-ocimene Natural products CC(=C)CCC=C(C)C=C XJPBRODHZKDRCB-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009692 water atomization Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
-
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
-
- 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
- C09D11/52—Electrically conductive inks
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
-
- 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
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
-
- 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
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
-
- 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
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0263—Details about a collection of particles
- H05K2201/0266—Size distribution
-
- 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
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0263—Details about a collection of particles
- H05K2201/0272—Mixed conductive particles, i.e. using different conductive particles, e.g. differing in shape
Definitions
- the present invention relates to a conductive ink composition and a method for forming an electrode using the same. More specifically, the present invention relates to a conductive ink composition which can be fired at low temperature so as to be formed into an electrode on a substrate or the like by a simple, environmentally friendly screen printing process, makes it possible to avoid or minimize the deformation (particularly shrinkage) of the substrate during firing in the electrode forming process, can ensure excellent pr intabi 1 ity, enables the electrode to have low linear resistance, and is relatively inexpensive, and a method for forming an electrode using the conductive ink composition.
- IC integrated circuit
- LCDs liquid crystal displays
- PDPs plasma display panels
- organic transistors organic transistors
- smart cards antennas
- cells or fuel cells sensors
- touch screens printed circuit boards
- PCBs printed circuit boards
- FPCBs flexible printed circuit board
- FIG. 1 is a flowchart showing schematically showing a process of fabricating a flexible printed circuit board (FPCB) by photolithography according. to the prior art.
- FPCB flexible printed circuit board
- the process of fabricating a flexible printed circuit board (FPCB) by photolithography generally comprises the steps of: i) providing a flexible copper clad laminate (FCCL) on a thin insulating film; ii) applying a photosensitive composition to the surface of the flexible copper clad laminate (FCCL), on which an electrode is to be formed, and drying the applied photosensitive composition, thereby forming a photosensitive film layer; iii) exposing the photosensitive film layer to light according to the pattern of the electrode to be formed; iv) removing the exposed or unexposed portion of the photosensitive film layer by a developer according to the pattern of the electrode to be formed; v) etching out the portion of the copper clad laminate, exposed by the development step according to the pattern of the electrode to be formed; and vi) removing the remaining photosensitive film layer.
- step iv) development
- step v) etching
- step vi) removal of the remaining photosensitive film layer
- inkjet printing is a process in which an electrode is formed by spraying a conductive ink composition, which comprises conductive metal particles and has relatively low viscosity so as to be able to be inkjet- printed, on a substrate according to the pattern of the electrode to be formed, and drying or firing the sprayed composition.
- this inkjet •printing process has a problem in that, because the conductive ink composition is excessively shrunk and has low viscosity, it is difficult to ensure the thickness of the electrode formed, and thus it is difficult to provide an electrode having low linear resistance.
- FIG. 2 is a flowchart schematically showing a process of fabricating a flexible printed circuit board (FPCB) by screen printing.
- FPCB flexible printed circuit board
- the process of fabricating a flexible printed circuit board (FPCB) by screen printing generally comprises the steps of: i) providing a flexible base substrate made of a polymer resin such as polyimide or polyester; ii) applying a conductive ink composition, which is in the form of a paste having relatively high viscosity and comprises conductive metal particles, on the base substrate using a screen according to the pattern of the electrode to be formed; and iii) firing the applied conductive ink composition at high temperature and sintering the conductive metal particles contained in the composition, thereby forming an electrode.
- a conductive ink composition which is in the form of a paste having relatively high viscosity and comprises conductive metal particles
- the screen printing process is a relatively simple process consisting of a total of 3 steps, and thus has an advantage in that equipment costs and processing costs are reduced.
- this process has an advantage in that it is environmentally friendly, because it does not comprise a photosensitive material removing step, a copper clad laminate etching step, and the like, which cause environmental pollution.
- the screen printing process uses a conductive ink composition which in the form of a paste having relatively high viscosity, and thus it is advantageous in that it is possible to ensure the thickness of the electrode to be formed, thus achieving an electrode having low linear resistance.
- the conductive ink composition applied to the base substrate made of polyimide or polyester is fired at a high temperature of 200 to 350 ° C in an atmosphere of inert gas so as to inhibit oxidation of the metal particles contained in the ⁇ compos it ion.
- the firing process that is performed in an atmosphere of inert gas is complicated, and when the conductive ink composition is fired at high temperature, the deformation (particularly shrinkage) of the base substrate may occur.
- the diameter of the conductive metal particles contained in the conductive ink composition is reduced in order to lower the firing temperature that is used in the process of forming an electrode by screen printing, the uniform dispersion of the conductive metal particles in the conductive ink composition, the storage stability of the conductive ink composition, the electrical conductivity of the electrode formed, etc., cannot be guaranteed.
- the conductive ink composition is exposed to air, water, high temperature, oxidizing agents or the like, the conductive metal particles will be oxidized so that the electrical conductivity of the electrode to be formed significantly decreases.
- the diameter of the conductive metal particles is increased in order to ensure the uniform of the conductive metal particles, the inhibition of oxidization of the particles, the storage stability of the conductive ink composition, the high electrical conductivity of the electrode formed, etc., the sintering temperature of the conductive metal particles will significantly increase.
- Korean Patent Laid-Open Publication No. 2011-0049466 discloses a conductive adhesive which comprises conductive particles having a core-shell structure, low-melting-point alloy powder, nanopowder, etc.
- a process for preparing the conductive particles having the core-shell structure is complicated.
- the particle sizes of the conductive particles, alloy power, nanopowder and the like contained in the conductive adhesive are too small (10-100 nm), it is difficult to achieve the uniform dispersion of the particles in the conductive adhesive, the storage stability of the conductive adhesive, the desired electrical conductivity, etc.
- Korean Patent Laid-Open Publication No. 2012-0115444 discloses the use of a mixture of a submicron-sized conductive filler and a nanosized conductive filler to achieve high electrical conductivity together with low firing temperature.
- high electrical conductivity and low firing temperature cannot be simultaneously achieved at a desired level, only by control of the diameter of conductive metal particles that are added.
- Korean Patent Laid-Open Publication No. 2010-0110889 discloses the use of submicron-sized core-shell metal particles and another kind of submicron-sized metal particles, wherein the metals of the metal particles have relatively low melting points, and the firing temperature in the electrode forming process is lowered by an eutectic reaction between tin, a tin alloy or the like, which constitutes the shell of the core-shell metal particles, and bismuth, indium, a bismuth alloy or the like, which constitutes the other metal particles.
- a process for preparing the core-shell metal particles is complicated, and the low-melting-point metals are costly and have low electrical conductivity.
- the metal particles are all submicron-sized particles, and thus the firing temperature cannot be sufficiently lowered.
- Another object of the present invention is to provide a conductive ink composition which can be fired at low temperature and atmospheric pressure in a process of forming an electrode on a flexible substrate made of polyimide resin, polyester resin or the like by screen printing so as to make it possible to avoid or minimize the deformation of the flexible substrate, and at the same time, enables the electrode to have high electrical conductivity even when the composition is fired at low temperature, and a method for forming an electrode using the conductive ink composition.
- Still another object of the present invention is to provide a conductive ink composition which is relatively inexpensive, and a method for forming an electrode using the conductive ink composition.
- Yet another object of the present invention is to provide a conductive ink composition which shows excellent printability in a process of forming an electrode by screen printing so as to ensure the thickness of the electrode formed and enable the electrode to have low linear resistance, and a method for forming an electrode using the conductive ink composition.
- the submicron-sized copper (Cu) particles which have a median weight in the particle size distribution based on the copper (Cu) particles' weights, may have a mean diameter (D 50 ) of 350-380 nm
- the nano-sized silver (Ag) particles which have a median weight in the particle size distribution based on the silver (Ag) particles' weights, may have a mean diameter (D 50 ) of 100 nm or smaller.
- the copper (Cu) particles may be surface-treated with at least one surface treatment agent selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organic metal compound salts, polyani 1 ine-based resins, and metal alkoxides.
- the copper (Cu) particles have a spherical shape, a flat shape or a plate shape.
- the binder may be selected from the group consisting of cellulose-based resin, polyvinyl chloride resin or its copolymer, polyvinyl alcohol-based resin, polyvinyl pyrrol idone-based resin, acrylic resin, a vinyl acetate- acrylic acid ester copolymer, butyral resin, alkyd resin, epoxy resin, phenol resin, rosin ester resin, polyester resin, and a mixture of two or more thereof.
- the binder is polyester resin
- the organic solvent is a 5:5 to 8:2 mixture of a-terpineol and butyl acetate.
- the organic solvent may be selected from the group consisting of hydrocarbon solvents, chlorinated hydrocarbon solvents, cyclic ether solvents, amide solvents, ketone solvents, alcohol or polyhydric alcohol solvents, acetate solvents, polyhydric alcohol ether solvents, terpene solvents, and a mixture of two or more thereof.
- the conductive ink composition may further comprise a phosphorus- containing compound, a flux, a plasticizer, a dispersing agent, a surfactant, an inorganic binder, a metal oxide, a ceramic material, an organic metal compound, or a mixture of two or more thereof.
- the composition may have a thixotropic index of 4-6.
- a method for forming an electrode comprising the steps of: placing in a screen printing frame a base substrate in which the electrode is to be formed; placing on the base substrate a silk, nylon, polyester or metal screen having open areas formed according to the pattern of the electrode to be formed; forcing the conductive ink composition of claim 1 or 2 through the open areas of the screen with a squeegee to apply the conductive ink composition to the base substrate according to the electrode pattern; and drying and firing the conductive ink composition, applied to the base substrate, at a temperature of 150 to 200 ° C for 30-60 minutes, thereby forming the electrode.
- the formed electrode may have a thickness of 10-25 pm and a linear
- a conductive ink composition according to the present invention comprises a specific combination of conductive metal particles at a specific mixing ratio so that it can be fired at low temperature and atmospheric pressure in a process of forming an electrode on a flexible substrate made of resin such as polyimide or polyester so as to make it possible to avoid or minimize the deformation of the flexible substrate, and at the same time, enables the electrode to have high electrical conductivity.
- the conductive ink composition according to the present invention can be formed into an electrode by screen printing in place of a conventional photolithography process which is complicated and not environmentally friendly.
- the conductive ink composition according to the present invention is inexpensive, because it comprises relatively inexpensive conductive metal particles.
- the conductive ink composition according to the present invention comprises a specific combination of conductive metal particles, a binder, a solvent and the like at a specific mixing ratio so that it shows excellent printability in a process of forming an electrode by screen printing, and thus ensures the thickness of the electrode and enables the electrode to have low linear resistance.
- FIG. 1 is a flowchart schematically showing a process of fabricating a flexible printed circuit board (FPCB) by a conventional photolithography process.
- FPCB flexible printed circuit board
- FIG. 2 is a flowchart schematically showing a process of fabricating a flexible printed circuit board (FPCB) by a conventional screen printing process.
- FPCB flexible printed circuit board
- FIG. 3 is a scanning electron microscope (SEM) photograph of the inventive conductive ink composition before firing.
- FIG. 4 is a SEM photograph of the inventive conductive ink composition after firing at 200 ° C for 30 minutes.
- a conductive ink composition according to the present invention may comprise conductive ink particles, a binder and an organic solvent.
- the conductive metal particles may include metal particles of at least two metal elements selected from among metal elements belonging to Groups 10 to 12 of the periodic table. Specifically, the conductive metal particles may include first metal particles having a submicron size and second metal particles having a nanometer size. Preferably, the first metal particles may be copper (Cu) particles, and the second metal particles may be silver (Ag) particles.
- a copper (Cu) precursor for obtaining copper (Cu) particles corresponding to the first metal particles is not specifically limited, and examples thereof include CuCl, CuCl 2 , Cu(acac)2, Cu(hfac) 2 , Cu(tfac) 2 ,
- the copper (Cu) particles can be prepared from the copper (Cu) precursor by a conventional method for preparing metal particles or fine particles, for example, a water atomization method or a wire electrical explosion method.
- a firing process for forming an electrode from a conductive composition comprising the copper (Cu) particles as conductive metal particles should be carried out in an atmosphere of inert gas such as nitrogen.
- the copper (Cu) particles may be copper alloy particles containing P, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al , Zr , W, Mo, Ti, Co, Ni, Au or the like, or may be surface- treated with at least one compound selected from among surface treatment agents, including triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organic metal compound salts, polyani 1 ine-based resins, and metal alkoxides.
- surface treatment agents including triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organic metal compound salts, polyani 1 ine-based resins, and metal alkoxides.
- Examples of the triazole compound that is used to treat the surface of the copper (Cu) particles in order to improve the oxidation resistance thereof include benzotr iazole and triazole.
- examples of the saturated fatty acid include enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, stearic acid, nonadecanoic acid, arachic acid, and behenic acid.
- examples of the unsaturated fatty acid include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, cetoleic acid, brassidic acid, erucic acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
- examples of the inorganic metal compound salt include sodium silicate, sodium stannate, tin sulfate, zinc sulfate, sodium zincate, zirconium nitrate, sodium zirconate, zirconium oxide chloride, titanium sulfate, titanium chloride, and potassium oxalate titanate.
- examples of the organic metal compound salt include lead stearate, lead acetate, a p-cumylphenyl derivative of tetraalkoxyzirconium, and a p-cumylphenyl derivative of tetraalkoxytitanium.
- examples of the metal alkoxide include titanium alkoxide, zirconium alkoxide, lead alkoxide, silicon alkoxide, tin alkoxide, and indium alkoxide.
- the copper (Cu) particles that are to be surface-treated with the surface treatment agent may include copper (Cu) alloy particles.
- Surface- treated copper (Cu) particles can be prepared using a surface treatment solution prepared by dissolving 1-90 wt% of the surface treatment agent in a solvent capable of dissolving the surface treatment agent.
- the solvent include water, alcohol-based solvents such as methanol, ethanol, and isopropanol, glycol-based solvents such as ethylene glycol monoethyl ether, carbitol-based solvents such as diethylene glycol monobutyl ether, and carbitol acetate-based solvents such as diethylene glycol monoethyl ether acetate.
- the peak temperature in the exothermic peak showing a maximum area may be 280 ° C or higher, preferably 290 to 750 ° C , and more preferably 350 to 750 ° C .
- the conductive ink composition according to the present invention comprises such copper (Cu) particles as the first metal particles, the oxidation of the copper (Cu) particles during firing in the electrode forming process can be inhibited so that an electrode having high electrical conductivity can be formed.
- the copper (Cu) particles which have a median weight in the particle size distribution based on the copper (Cu) particles' weights, may have a mean diameter (D 50 ) of 350 to 380 nm.
- D 50 mean diameter of the copper (Cu) particles
- nanosized silver (Ag) particles as the second metal particles can be attached to the surface of the copper (Cu) particles to effectively inhibit the oxidation of the copper particles, and when it is less than 380 nm or smaller, the contact area between the copper (Cu) particles in the electrode formed can increase so that the electrical conductivity of the electrode can be effectively increased even when the firing process is carried out at low temperature.
- the shape of the copper (Cu) particles is not particularly limited, and it may be, for example, a spherical shape, a flat shape, a block shape, a plate shape, a scale-like shape or the like. From the viewpoint of oxidation resistance and electrical conductivity, the shape of the copper (Cu) particles is preferably a spherical shape, a flat shape, or a plate shape. Meanwhile, the copper (Cu) particles corresponding to the first metal particles are abundant in nature, and thus the price thereof is as low as about 1/100 of that of silver (Ag).
- a silver (Ag) precursor for obtaining silver (Ag) particles that are the second metal particles is not specifically limited, and examples thereof include Ag(N0 3 ), Ag 2 (S0 4 ), Ag(BF 4 ) , Ag(PF 6 ), Ag 2 0, CH 3 C0OAg, Ag(CF 3 S0 3 ),
- the silver (Ag) particles may include
- the silver (Ag) particles can be prepared from the silver (Ag) precursor by a conventional method such as a wet reduction method.
- silver (Ag) particles can be prepared by dissolving silver in nitric acid, sulfuric acid or the like to prepare a silver precursor such as Ag(N0 3 ) or Ag 2 (S0 4 ), diluting the silver precursor in distilled water, adding ammonia water thereto to prepare a complex compound, adding a dispersing agent to the complex compound to prepare a mono-dispersed silver complex compound, reducing the silver complex compound with a reducing agent, and washing the reduced compound with an organic solvent and distilled water.
- a silver precursor such as Ag(N0 3 ) or Ag 2 (S0 4 )
- the silver (Ag) particles which have a median weight in the particle size distribution based on the silver (Ag) particles' weights, may have a mean diameter (D 5 o) of 100 nm or less, preferably 10-100 nm.
- D 5 o mean diameter of 100 nm or less
- the mean diameter (D 50 ) of the silver (Ag) particles is 10 nm or larger, the particles will have improved storage stability, and when it is 100 nm or smaller, the conductive ink composition according to the present invention can be fired at low temperature while pores will be formed between submicron- sized copper (Cu) particles as the first metal particles and serve as bridges between the copper (Cu) particles during the firing process, thereby improving the electrical conductivity of the electrode.
- the shape of the silver (Ag) particles is not particularly limited, and it may be, for example, a spherical shape, a flat shape, a block shape, a plate shape, a scale-like shape or the like. Preferably, it may be a spherical shape, a flat shape, or a plate shape.
- the conductive ink composition according to the present invention comprises copper (Cu) particles as first metal particles and silver (Ag) particles as second metal particles, wherein the mean diameter (D 50 ) of the copper (Cu) particles as the first metal particles may be submicron-sized (350-380 run), and the mean diameter (D 50 ) of the silver
- (Ag) particles as the second metal particles may be nano-sized (100 nm or smaller).
- the conductive ink composition according to the present invention comprises the submicron-sized copper (Cu) particles to ensure the high electrical conductivity of the electrode formed. Also, because the nano-sized silver (Ag) particles serve as bridges between the copper (Cu) particles during firing in the electrode forming process, the conductive ink composition can be fired at low temperature. Further, because the silver (Ag) particles are attached to the copper (Cu) particles to further inhibit the oxidation of the copper (Cu) particles, the firing process does not need to be carried out in an atmosphere of inert gas.
- the conductive ink composition of the present invention does not cause clogging so that it can be printed over large areas, and thus is advantageous for mass production.
- the mixing ratio of the copper (Cu) particles as the first metal particles to the silver (Ag) particles as the second metal particles may be 70:30 to 80:20.
- the conductive ink composition is inexpensive, because it comprises a significant amount of the conductive copper (Cu) particles that are significantly inexpensive compared to the silver (Ag) particles.
- the copper (Cu) particles have a melting point of 1084.6 ° C
- the silver (Ag) particles have a melting point of 961 V
- the metal particle mixture will have a melting point of about 779 °C , which is lower than the melting point of each of the metal particles before mixing.
- This low melting point is defined as eutectic point.
- the conductive ink composition according to the present invention can be fired at a low temperature of 150 to 200 °C by virtue of the eutectic point resulting from the specific mixing ratio between the copper (Cu) particles and the silver (Ag) particles. Despite firing at this low temperature, the electrode formed from the conductive ink composition can have high electrical conductivity.
- FIG. 3 is a scanning electron microscope (SEM) photograph of the conductive ink composition according to the present invention before firing it
- FIG. 4 is a scanning electron microscope (SEM) photograph of the inventive conductive ink composition after firing at low temperature.
- SEM scanning electron microscope
- nano-sized silver (Ag) particles are interposed between submicron- sized copper (Cu) particles to form bridges therebetween, and furthermore, a low eutectic point is achieved by the specific mixing ratio between the copper (Cu) particles and the silver (Ag) particles, suggesting that the metal particles contained in the composition can be sintered even when they are fired even at low temperature.
- the conductive ink composition according to the present invention may further comprise a suitable binder in order to ensure the uniform dispersion of the first metal particles and the second metal particles, the excellent printability of the composition by control of the viscosity and thixotropic index thereof, and the close adhesion of an electrode to a flexible substrate made of a material such as polyimide or polyester in a process of applying the composition to the flexible substrate to form the electrode.
- a suitable binder in order to ensure the uniform dispersion of the first metal particles and the second metal particles, the excellent printability of the composition by control of the viscosity and thixotropic index thereof, and the close adhesion of an electrode to a flexible substrate made of a material such as polyimide or polyester in a process of applying the composition to the flexible substrate to form the electrode.
- the binder is not specifically limited and may be, for example, cellulose-based resin such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose or nitrocellulose, polyvinyl chloride resin or its copolymer, polyvinyl alcohol resin, polyvinyl pyrrol idone resin, acrylic resin such as polymethylmethacrylate, a vinyl acetate-acrylic acid ester copolymer resin, butyral resin such as polyvinyl butyral, alkyd resin such as phenol modified alkyd resin or castor oil fatty acid modified alkyd resin, epoxy resin, phenol resin, rosin ester resin, polyester resin, or a combination of two or more thereof.
- the binder that is used in the present invention is preferably polyester resin having high viscosity in order to ensure the excellent printability of the inventive conductive ink composition by control of the viscosity and thixotropic index thereof.
- the content of the binder may be 2-10 parts by weight based on 100 parts by weight of the conductive metal particles contained in the inventive conductive ink composition. If the content of the binder is less than 2 parts by weight, the viscosity of the conductive ink composition will be excessively reduced, making it difficult to prepare a paste-type composition for screen printing, and if the content of the binder is more than 10 parts by weight, the viscosity and thixotropic index of the conductive ink composition will be excessively increased, resulting in an increase in the linear resistance of the electrode formed and a decrease in the electrical conduct ivity.
- the conductive ink composition according to the present invention may further comprise a suitable organic solvent in order to ensure the uniform dispersion of the first and second metal particles, the excellent printability of the composition by control of the viscosity and thixotropic index thereof, and the processabi 1 ity and workability of the composition in the electrode forming process.
- the organic solvent is not specifically limited, and examples thereof
- hydrocarbon solvents such as hexane, cyclohexane, and toluene
- chlorinated hydrocarbon solvents such as dichloroethylene, dichloroethane, and dichlorobenzene!
- cyclic ether solvents such as tetrahydrofuran, furan, tetrahydropyran, pyran, dioxane, 1,3-dioxolane, and trioxane!
- an amide solvent such as ⁇ , ⁇ -dimethylformamide, and ⁇ , ⁇ -dimethylacetamide
- sulfoxide solvents such as dimethylsulfoxide, and diethylsulfoxide
- ketone solvents such as acetone, methyl ethyl ketone, diethylketone, and cyclohexanone
- alcohol or polyhydric alcohol solvents such as ethanol, 2-propanol, 1- butanol, diacetone alcohol, and glycol
- acetate solvents such as butyl acetate, 2,2,4-tr imethyl-l,3-pentanediol monoacetate, 2,2,4-tr imethyl-1, 3- pentanediol monopropionate, 2,2,4-tr imethyl-l,3-pentanediol monobutyrate, 2,2,4-trimethyl-l,3-pentanediol monoisobutyrate (Texan
- the organic solvent that is used in the present invention includes a high-boiling-point organic solvent such as a-terpineol (boiling point: 219 °C). If the boiling point of the organic solvent during firing in the electrode forming process is low, the organic solvent will be rapidly volatilized so that it is removed before sintering of the conductive metal particles contained in the applied conductive ink composition, and thus an electrode cannot be formed from the composition.
- a high-boiling-point organic solvent such as a-terpineol (boiling point: 219 °C). If the boiling point of the organic solvent during firing in the electrode forming process is low, the organic solvent will be rapidly volatilized so that it is removed before sintering of the conductive metal particles contained in the applied conductive ink composition, and thus an electrode cannot be formed from the composition.
- the organic solvent may include a combination of a-terpinene and butyl acetate at a ratio of 5:5 to 8:2 in order to ensure processabi lity and workability in the electrode forming process, as well as the excellent printability of the inventive conductive ink composition by control of the viscosity and thixotropic index thereof.
- the content of the organic solvent may be 5-20 parts by weight based on
- the conductive metal particles contained in the conductive ink composition of the present invention 100 parts by weight of the conductive metal particles contained in the conductive ink composition of the present invention. If the content of the organic solvent is less than 5 parts by weight, it will be difficult to prepare a paste type composition for screen printing, and if the content of the organic solvent is more than 20 parts by weight, the thixotropic index of the conductive ink composition will be excessively reduced to cause spreading after printing, suggesting that the composition has poor printability.
- the conductive ink composition according to the present invention may further comprise a phosphorus-containing compound, a flux or other additives.
- the phosphorus-containing compound and the flux can further increase the oxidation resistance of the conductive ink composition of the conductive ink composition and the electrical conductivity of the electrode formed.
- the phosphorus-containing compound include phosphorus-based inorganic acids such as phosphoric acid; phosphates such as ammonium phosphate * , phosphoric acid esters such as phosphoric acid alkyl ester or phosphoric acid aryl ester; cyclic phosphazenes such as hexaphenoxyphosphazene ; or derivatives thereof.
- the content of the phosphorus-containing compound may be 0.5-10 parts by weight based on the total weight of the conductive ink composition.
- Examples of the flux include fatty acids, boronic acid compounds, fluoride compounds, and borofluoride compounds, for example, lauric acid, myristic acid, palmitic acid, stearic acid, sorbic acid, stearolic acid, boron oxide, potassium borate, sodium borate, lithium borate, potassium borofluoride, sodium borofluoride, lithium borofluoride, acidic potassium fluoride, acidic sodium fluoride, acidic lithium fluoride, potassium fluoride, sodium fluoride, lithium fluoride, lithium fluoride, etc.
- the content of the flux may be 0.1-5 parts by weight based on the total weight of the conductive ink composition.
- Examples of the other additives include plast icizers, dispersing agents, surfactants, inorganic binders, metal oxides, ceramic materials, organic metal compounds, etc.
- the conductive ink composition according to the present invention can be prepared by any method.
- it can be prepared by dispersing and mixing the first metal particles, the second metal particles, the binder and the organic solvent, optionally the phosphorus-containing compound, the flux and other additives, using conventional dispersing and mixing methods.
- the conductive ink composition according to the present invention preferably has a thixotropic index of 4-6 depending on the kind of conductive metal particles, binder, organic solvent and the like therein and the mixing ratio therebetween.
- the present invention is directed to a method of forming an electrode in a liquid crystal display (LCD), a plasma display panel (PDP), an organic transistor, a smart card, an antenna, a cell, a fuel cell, a sensor, a touch screen, a printed circuit board (PCB), particularly a flexible printed circuit board (FPCB), etc., by screen printing using the conductive ink composition of the present invention.
- LCD liquid crystal display
- PDP plasma display panel
- organic transistor organic transistor
- smart card an antenna
- PCB printed circuit board
- FPCB flexible printed circuit board
- the inventive method for forming an electrode comprises the steps of: i) placing in a screen printing frame a base substrate in which the electrode is to be formed; ii) placing on the base substrate a silk, nylon, polyester or metal screen having open areas formed according to the pattern of the electrode to be formed; iii) forcing the conductive ink composition of the present invention through the open areas of the screen with a squeegee to apply the conductive ink composition to the base substrate according to the electrode pattern; and iv) drying and firing the conductive ink composition, applied to the base substrate, at a temperature of 150 to 200 ° C for 30-60 minutes, thereby forming the electrode.
- the base substrate may be a base substrate which is used in a liquid crystal display (LCD), a plasma display panel (PDP), an organic transistor, a smart card, an antenna, a cell, a fuel cell, a touch screen, a printed circuit board (PCB), particularly a flexible printed circuit board (FPCB), etc.
- LCD liquid crystal display
- PDP plasma display panel
- organic transistor organic transistor
- smart card an antenna
- cell a cell
- fuel cell a fuel cell
- a touch screen a touch screen
- PCB printed circuit board
- FPCB flexible printed circuit board
- the electrode formed as described above may have a
- Silver (Ag) particles manufactured by LS Cable & System, Korea; product name: silver nanopart icles (prepared by a wet reduction method and capped with oleic acid)
- Comparative Examples was screen-printed on a polyimide substrate to form an applied portion having a size of 1 cm (width) x 10 cm (length), and was then fired (dried) at 200 ° C in an air atmosphere for 30 minutes.
- the linear resistance and thixotropic index of the dried or fired printed electrode were measured, and the results of the measurement are shown in Table 2 below. [Table 2]
- the conductive ink compositions of Examples 1 and 2 were fired at a low temperature of 200 ° C , the nano-sized silver (Ag) particles were interposed between the submicron- sized copper (Cu) particles in the composition to form bridges therebetween. Also, as shown in FIG. 4, the metal particles were easily sintered due to a low eutectic point resulting from the specific mixing ratio of the copper (Cu) particles to the silver (Ag) particles.
- the electrodes formed from the conductive ink compositions had a thixotropic index of 4.5 or
- Example 1 containing submicron-sized copper (Cu) particles without containing nano-sized silver (Ag) particles and the conductive ink composition of Comparative Example 2 containing a very small amount of nano-sized silver (Ag) particles, the formation of bridges between the copper (Cu) particles by the nano-sized silver (Ag) particles did not occur or was insufficient, and the low eutectic point of the particle mixture could not be achieved.
- the conductive ink compositions of the Comparative Examples were fired at a low temperature of 200 ° C , sintering of the metal particles did not substantially occur, and the resulting electrodes had a linear resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Conductive Materials (AREA)
Abstract
The present invention relates to a conductive ink composition and a method for forming an electrode using the same. More specifically, the present invention relates to a conductive ink composition which can be fired at low temperature so as to be formed into an electrode on a substrate or the like by a simple, environmentally friendly screen printing process, makes it possible to avoid or minimize the deformation (particularly shrinkage) of the substrate during firing in the electrode forming process, can ensure excellent printability, enables the electrode to have low linear resistance, and is relatively inexpensive, and a method for forming an electrode using the conductive ink composition.
Description
[DESCRIPTION]
[Invent ion Tit le]
CONDUCTIVE INK COMPOSITION AND METHOD FOR FORMING ELECTRODE USING THE
SAME
[Technical Field]
<i> The present invention relates to a conductive ink composition and a method for forming an electrode using the same. More specifically, the present invention relates to a conductive ink composition which can be fired at low temperature so as to be formed into an electrode on a substrate or the like by a simple, environmentally friendly screen printing process, makes it possible to avoid or minimize the deformation (particularly shrinkage) of the substrate during firing in the electrode forming process, can ensure excellent pr intabi 1 ity, enables the electrode to have low linear resistance, and is relatively inexpensive, and a method for forming an electrode using the conductive ink composition.
[Background Art]
<2> Generally, photolithography has been used to form electrodes or integrated circuit (IC) chips in liquid crystal displays (LCDs), plasma display panels (PDPs), organic transistors, smart cards, antennas, cells or fuel cells, sensors, touch screens, printed circuit boards (PCBs), particularly flexible printed circuit board (FPCBs), etc.
<3> FIG. 1 is a flowchart showing schematically showing a process of fabricating a flexible printed circuit board (FPCB) by photolithography according. to the prior art.
<4> As shown in FIG. 1, the process of fabricating a flexible printed circuit board (FPCB) by photolithography generally comprises the steps of: i) providing a flexible copper clad laminate (FCCL) on a thin insulating film; ii) applying a photosensitive composition to the surface of the flexible copper clad laminate (FCCL), on which an electrode is to be formed, and drying the applied photosensitive composition, thereby forming a photosensitive film layer; iii) exposing the photosensitive film layer to light according to the pattern of the electrode to be formed; iv) removing
the exposed or unexposed portion of the photosensitive film layer by a developer according to the pattern of the electrode to be formed; v) etching out the portion of the copper clad laminate, exposed by the development step according to the pattern of the electrode to be formed; and vi) removing the remaining photosensitive film layer.
<5> As described above, the process of fabricating the flexible printed circuit board (FPCB) by photolithography consists of a total of six steps, and this complex process requires high equipment costs and processing costs. In addition, step iv) (development), step v) (etching) and step vi) (removal of the remaining photosensitive film layer) cause the loss of materials and the generation of non-environmental ly friendly materials.
<6> Due to these problems of photolithography, screen printing, inkjet printing or the like has been used as an alternative to photolithography.
<7> Herein, inkjet printing is a process in which an electrode is formed by spraying a conductive ink composition, which comprises conductive metal particles and has relatively low viscosity so as to be able to be inkjet- printed, on a substrate according to the pattern of the electrode to be formed, and drying or firing the sprayed composition. However, this inkjet •printing process has a problem in that, because the conductive ink composition is excessively shrunk and has low viscosity, it is difficult to ensure the thickness of the electrode formed, and thus it is difficult to provide an electrode having low linear resistance.
<8> Meanwhile, FIG. 2 is a flowchart schematically showing a process of fabricating a flexible printed circuit board (FPCB) by screen printing.
<9> As shown in FIG. 2, the process of fabricating a flexible printed circuit board (FPCB) by screen printing generally comprises the steps of: i) providing a flexible base substrate made of a polymer resin such as polyimide or polyester; ii) applying a conductive ink composition, which is in the form of a paste having relatively high viscosity and comprises conductive metal particles, on the base substrate using a screen according to the pattern of the electrode to be formed; and iii) firing the applied conductive ink composition at high temperature and sintering the conductive metal particles
contained in the composition, thereby forming an electrode.
<io> Unlike the photolithography process according to the prior art, the screen printing process is a relatively simple process consisting of a total of 3 steps, and thus has an advantage in that equipment costs and processing costs are reduced. In addition, this process has an advantage in that it is environmentally friendly, because it does not comprise a photosensitive material removing step, a copper clad laminate etching step, and the like, which cause environmental pollution. Further, unlike the inkjet printing process according to the prior art, the screen printing process uses a conductive ink composition which in the form of a paste having relatively high viscosity, and thus it is advantageous in that it is possible to ensure the thickness of the electrode to be formed, thus achieving an electrode having low linear resistance.
<n> In the screen printing process, the conductive ink composition applied to the base substrate made of polyimide or polyester is fired at a high temperature of 200 to 350 °C in an atmosphere of inert gas so as to inhibit oxidation of the metal particles contained in the · compos it ion. However, there are shortcomings in that the firing process that is performed in an atmosphere of inert gas is complicated, and when the conductive ink composition is fired at high temperature, the deformation (particularly shrinkage) of the base substrate may occur.
ii2> Meanwhile, when the diameter of the conductive metal particles contained in the conductive ink composition is reduced in order to lower the firing temperature that is used in the process of forming an electrode by screen printing, the uniform dispersion of the conductive metal particles in the conductive ink composition, the storage stability of the conductive ink composition, the electrical conductivity of the electrode formed, etc., cannot be guaranteed. In addition, when the conductive ink composition is exposed to air, water, high temperature, oxidizing agents or the like, the conductive metal particles will be oxidized so that the electrical conductivity of the electrode to be formed significantly decreases. On the other hand, when the diameter of the conductive metal particles is increased
in order to ensure the uniform of the conductive metal particles, the inhibition of oxidization of the particles, the storage stability of the conductive ink composition, the high electrical conductivity of the electrode formed, etc., the sintering temperature of the conductive metal particles will significantly increase.
<i3> Thus, there have been attempts to overcome the shortcomings of the screen printing process while maintaining the advantages.
<i4> For example, Korean Patent Laid-Open Publication No. 2011-0049466 discloses a conductive adhesive which comprises conductive particles having a core-shell structure, low-melting-point alloy powder, nanopowder, etc. However, it has a problem in that a process for preparing the conductive particles having the core-shell structure is complicated. In addition, because the particle sizes of the conductive particles, alloy power, nanopowder and the like contained in the conductive adhesive are too small (10-100 nm), it is difficult to achieve the uniform dispersion of the particles in the conductive adhesive, the storage stability of the conductive adhesive, the desired electrical conductivity, etc.
<i5> Further, Korean Patent Laid-Open Publication No. 2012-0115444 discloses the use of a mixture of a submicron-sized conductive filler and a nanosized conductive filler to achieve high electrical conductivity together with low firing temperature. However, it was experimentally demonstrated by the present inventors that high electrical conductivity and low firing temperature cannot be simultaneously achieved at a desired level, only by control of the diameter of conductive metal particles that are added.
i6> In addition, Korean Patent Laid-Open Publication No. 2010-0110889 discloses the use of submicron-sized core-shell metal particles and another kind of submicron-sized metal particles, wherein the metals of the metal particles have relatively low melting points, and the firing temperature in the electrode forming process is lowered by an eutectic reaction between tin, a tin alloy or the like, which constitutes the shell of the core-shell metal particles, and bismuth, indium, a bismuth alloy or the like, which constitutes the other metal particles. However, a process for preparing the
core-shell metal particles is complicated, and the low-melting-point metals are costly and have low electrical conductivity. In addition, it was experimentally demonstrated by the present inventors that the metal particles are all submicron-sized particles, and thus the firing temperature cannot be sufficiently lowered.
<i7> Therefore, there is a need to provide a novel ink composition for forming an electrode, which can be fired at low temperature and atmospheric pressure in a process of forming the electrode by screen printing, can the high electrical conductivity of. the electrode even when it is fired at low temperature, is relatively inexpensive, and has excellent printability to ensure the thickness of the electrode formed and enable the electrode to have low linear resistance, and a method for forming an electrode using the ink compos i t i on .
[Disclosure]
[Technical Problem]
<i8> It is an object of the present invention to provide a conductive ink composition which can be formed into an electrode by a simple, environmentally friendly screen printing process, and a method for forming an electrode using the same.
;i9> Another object of the present invention is to provide a conductive ink composition which can be fired at low temperature and atmospheric pressure in a process of forming an electrode on a flexible substrate made of polyimide resin, polyester resin or the like by screen printing so as to make it possible to avoid or minimize the deformation of the flexible substrate, and at the same time, enables the electrode to have high electrical conductivity even when the composition is fired at low temperature, and a method for forming an electrode using the conductive ink composition.
o> Still another object of the present invention is to provide a conductive ink composition which is relatively inexpensive, and a method for forming an electrode using the conductive ink composition.
i> Yet another object of the present invention is to provide a conductive ink composition which shows excellent printability in a process of forming an
electrode by screen printing so as to ensure the thickness of the electrode formed and enable the electrode to have low linear resistance, and a method for forming an electrode using the conductive ink composition.
[Technical Solution]
<22> In accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of a conductive ink composition comprising conductive metal particles including submicron-sized copper (Cu) particles and nano-sized silver (Ag) particles at a ratio of copper (Cu): silver (Ag)=70:30 to 80:20, and, based on 100 parts by weight of the conductive metal particles, 2-10 parts by weight of a binder and 5-20 parts by weight of an organic solvent.
<23> The submicron-sized copper (Cu) particles, which have a median weight in the particle size distribution based on the copper (Cu) particles' weights, may have a mean diameter (D50) of 350-380 nm, and the nano-sized silver (Ag) particles, which have a median weight in the particle size distribution based on the silver (Ag) particles' weights, may have a mean diameter (D50) of 100 nm or smaller.
<24> The copper (Cu) particles may be surface-treated with at least one surface treatment agent selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organic metal compound salts, polyani 1 ine-based resins, and metal alkoxides.
<25> The copper (Cu) particles have a spherical shape, a flat shape or a plate shape.
;26> The binder may be selected from the group consisting of cellulose-based resin, polyvinyl chloride resin or its copolymer, polyvinyl alcohol-based resin, polyvinyl pyrrol idone-based resin, acrylic resin, a vinyl acetate- acrylic acid ester copolymer, butyral resin, alkyd resin, epoxy resin, phenol resin, rosin ester resin, polyester resin, and a mixture of two or more thereof. Furthermore, the binder is polyester resin, and the organic solvent is a 5:5 to 8:2 mixture of a-terpineol and butyl acetate.
ii> The organic solvent may be selected from the group consisting of
hydrocarbon solvents, chlorinated hydrocarbon solvents, cyclic ether solvents, amide solvents, ketone solvents, alcohol or polyhydric alcohol solvents, acetate solvents, polyhydric alcohol ether solvents, terpene solvents, and a mixture of two or more thereof.
<28> The conductive ink composition may further comprise a phosphorus- containing compound, a flux, a plasticizer, a dispersing agent, a surfactant, an inorganic binder, a metal oxide, a ceramic material, an organic metal compound, or a mixture of two or more thereof.
<29> The composition may have a thixotropic index of 4-6.
<30> And, in accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of a method for forming an electrode, the method comprising the steps of: placing in a screen printing frame a base substrate in which the electrode is to be formed; placing on the base substrate a silk, nylon, polyester or metal screen having open areas formed according to the pattern of the electrode to be formed; forcing the conductive ink composition of claim 1 or 2 through the open areas of the screen with a squeegee to apply the conductive ink composition to the base substrate according to the electrode pattern; and drying and firing the conductive ink composition, applied to the base substrate, at a temperature of 150 to 200 °C for 30-60 minutes, thereby forming the electrode.
<3i> The formed electrode may have a thickness of 10-25 pm and a linear
-5
resistance of 4X10 Ω · cm or less.
[Advantageous Effects]
<33> A conductive ink composition according to the present invention comprises a specific combination of conductive metal particles at a specific mixing ratio so that it can be fired at low temperature and atmospheric pressure in a process of forming an electrode on a flexible substrate made of resin such as polyimide or polyester so as to make it possible to avoid or minimize the deformation of the flexible substrate, and at the same time, enables the electrode to have high electrical conductivity.
<34> Moreover, the conductive ink composition according to the present invention can be formed into an electrode by screen printing in place of a conventional photolithography process which is complicated and not environmentally friendly.
<35> Further, the conductive ink composition according to the present invention is inexpensive, because it comprises relatively inexpensive conductive metal particles.
<36> In addition, the conductive ink composition according to the present invention comprises a specific combination of conductive metal particles, a binder, a solvent and the like at a specific mixing ratio so that it shows excellent printability in a process of forming an electrode by screen printing, and thus ensures the thickness of the electrode and enables the electrode to have low linear resistance.
[Description of Drawings]
;37> FIG. 1 is a flowchart schematically showing a process of fabricating a flexible printed circuit board (FPCB) by a conventional photolithography process.
38> FIG. 2 is a flowchart schematically showing a process of fabricating a flexible printed circuit board (FPCB) by a conventional screen printing process.
3 > FIG. 3 is a scanning electron microscope (SEM) photograph of the inventive conductive ink composition before firing.
ίθ> FIG. 4 is a SEM photograph of the inventive conductive ink composition after firing at 200 °C for 30 minutes.
[Mode for Invention]
<4i> A conductive ink composition according to the present invention may comprise conductive ink particles, a binder and an organic solvent.
<42> The conductive metal particles may include metal particles of at least two metal elements selected from among metal elements belonging to Groups 10 to 12 of the periodic table. Specifically, the conductive metal particles may include first metal particles having a submicron size and second metal particles having a nanometer size. Preferably, the first metal particles may be copper (Cu) particles, and the second metal particles may be silver (Ag) particles.
<43> A copper (Cu) precursor for obtaining copper (Cu) particles corresponding to the first metal particles is not specifically limited, and examples thereof include CuCl, CuCl2, Cu(acac)2, Cu(hfac)2, Cu(tfac)2,
Cu(dpm)2, Cu(ppm)2, Cu(fod)2, Cu(acim)2, Cu(nona-F)2, Cu(acen)2, Cu(N03)2 · 3H20,
CuS04 · 5H20 and the like. The copper (Cu) particles can be prepared from the copper (Cu) precursor by a conventional method for preparing metal particles or fine particles, for example, a water atomization method or a wire electrical explosion method.
<44> Because the copper (Cu) particles are likely to be oxidized at a temperature of 200 °C or higher, a firing process for forming an electrode from a conductive composition comprising the copper (Cu) particles as conductive metal particles should be carried out in an atmosphere of inert gas such as nitrogen. Thus, the copper (Cu) particles may be copper alloy particles containing P, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al , Zr , W, Mo, Ti, Co, Ni, Au or the like, or may be surface- treated with at least one compound selected from among surface treatment agents, including triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organic metal compound salts, polyani 1 ine-based resins, and metal alkoxides.
i5> Examples of the triazole compound that is used to treat the surface of the copper (Cu) particles in order to improve the oxidation resistance
thereof include benzotr iazole and triazole. Further, examples of the saturated fatty acid include enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, stearic acid, nonadecanoic acid, arachic acid, and behenic acid. Also, examples of the unsaturated fatty acid include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, cetoleic acid, brassidic acid, erucic acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. Moreover, examples of the inorganic metal compound salt include sodium silicate, sodium stannate, tin sulfate, zinc sulfate, sodium zincate, zirconium nitrate, sodium zirconate, zirconium oxide chloride, titanium sulfate, titanium chloride, and potassium oxalate titanate. In addition, examples of the organic metal compound salt include lead stearate, lead acetate, a p-cumylphenyl derivative of tetraalkoxyzirconium, and a p-cumylphenyl derivative of tetraalkoxytitanium. Additionally, examples of the metal alkoxide include titanium alkoxide, zirconium alkoxide, lead alkoxide, silicon alkoxide, tin alkoxide, and indium alkoxide.
<46> The copper (Cu) particles that are to be surface-treated with the surface treatment agent may include copper (Cu) alloy particles. Surface- treated copper (Cu) particles can be prepared using a surface treatment solution prepared by dissolving 1-90 wt% of the surface treatment agent in a solvent capable of dissolving the surface treatment agent. Examples of the solvent include water, alcohol-based solvents such as methanol, ethanol, and isopropanol, glycol-based solvents such as ethylene glycol monoethyl ether, carbitol-based solvents such as diethylene glycol monobutyl ether, and carbitol acetate-based solvents such as diethylene glycol monoethyl ether acetate.
<47> Generally, when pure copper (Cu) particles are subjected to simultaneous thermogravimetry-dif ferent ial thermal analysis (TG/DTA-6200, SI I Nanotechnology) at a measurement temperature ranging from room temperature to 1,000 °C at a heating rate of 40 °C/min and an atmospheric air flow rate of 200 l /min, the peak temperature in the exothermic peak showing a maximum
area is about 200 °C .
<48> However, when the copper (Cu) alloy particles or the surface-treated copper (Cu) particles, which are the first metal particles contained in the conductive ink composition according to the present invention is subjected to simultaneous thermogravimetry-di f f erent ial thermal analysis (TG-DTA) under the same conditions as described above, the peak temperature in the exothermic peak showing a maximum area may be 280 °C or higher, preferably 290 to 750 °C , and more preferably 350 to 750 °C . Because the conductive ink composition according to the present invention comprises such copper (Cu) particles as the first metal particles, the oxidation of the copper (Cu) particles during firing in the electrode forming process can be inhibited so that an electrode having high electrical conductivity can be formed.
<49> For example, the copper (Cu) particles, which have a median weight in the particle size distribution based on the copper (Cu) particles' weights, may have a mean diameter (D50) of 350 to 380 nm. When the mean diameter (D50) of the copper (Cu) particles is 350 nm or larger, nanosized silver (Ag) particles as the second metal particles can be attached to the surface of the copper (Cu) particles to effectively inhibit the oxidation of the copper particles, and when it is less than 380 nm or smaller, the contact area between the copper (Cu) particles in the electrode formed can increase so that the electrical conductivity of the electrode can be effectively increased even when the firing process is carried out at low temperature.
<50> In addition, the shape of the copper (Cu) particles is not particularly limited, and it may be, for example, a spherical shape, a flat shape, a block shape, a plate shape, a scale-like shape or the like. From the viewpoint of oxidation resistance and electrical conductivity, the shape of the copper (Cu) particles is preferably a spherical shape, a flat shape, or a plate shape. Meanwhile, the copper (Cu) particles corresponding to the first metal particles are abundant in nature, and thus the price thereof is as low as about 1/100 of that of silver (Ag).
5i> A silver (Ag) precursor for obtaining silver (Ag) particles that are the second metal particles is not specifically limited, and examples thereof
include Ag(N03), Ag2(S04), Ag(BF4) , Ag(PF6), Ag20, CH3C0OAg, Ag(CF3S03),
Ag(C104), AgCl, CH3C0CH=C0CH3Ag, etc. The silver (Ag) particles may include
Sb, Si, , Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl , V, Sn, Al, Zr, W, Mo, Ti , Co, Ni, Au or the like. The silver (Ag) particles can be prepared from the silver (Ag) precursor by a conventional method such as a wet reduction method. For example, silver (Ag) particles can be prepared by dissolving silver in nitric acid, sulfuric acid or the like to prepare a silver precursor such as Ag(N03) or Ag2(S04), diluting the silver precursor in distilled water, adding ammonia water thereto to prepare a complex compound, adding a dispersing agent to the complex compound to prepare a mono-dispersed silver complex compound, reducing the silver complex compound with a reducing agent, and washing the reduced compound with an organic solvent and distilled water.
<52> For example, the silver (Ag) particles, which have a median weight in the particle size distribution based on the silver (Ag) particles' weights, may have a mean diameter (D5o) of 100 nm or less, preferably 10-100 nm. When the mean diameter (D50) of the silver (Ag) particles is 10 nm or larger, the particles will have improved storage stability, and when it is 100 nm or smaller, the conductive ink composition according to the present invention can be fired at low temperature while pores will be formed between submicron- sized copper (Cu) particles as the first metal particles and serve as bridges between the copper (Cu) particles during the firing process, thereby improving the electrical conductivity of the electrode.
;53> In addition, the shape of the silver (Ag) particles is not particularly limited, and it may be, for example, a spherical shape, a flat shape, a block shape, a plate shape, a scale-like shape or the like. Preferably, it may be a spherical shape, a flat shape, or a plate shape.
54> As described above, the conductive ink composition according to the present invention comprises copper (Cu) particles as first metal particles and silver (Ag) particles as second metal particles, wherein the mean diameter (D50) of the copper (Cu) particles as the first metal particles may
be submicron-sized (350-380 run), and the mean diameter (D50) of the silver
(Ag) particles as the second metal particles may be nano-sized (100 nm or smaller).
<55> In other words, the conductive ink composition according to the present invention comprises the submicron-sized copper (Cu) particles to ensure the high electrical conductivity of the electrode formed. Also, because the nano-sized silver (Ag) particles serve as bridges between the copper (Cu) particles during firing in the electrode forming process, the conductive ink composition can be fired at low temperature. Further, because the silver (Ag) particles are attached to the copper (Cu) particles to further inhibit the oxidation of the copper (Cu) particles, the firing process does not need to be carried out in an atmosphere of inert gas. In addition, because the controlled diameters of the copper (Cu) particles and the silver (Ag) particles are smaller than those of conventional screen printing ink compositions, the conductive ink composition of the present invention does not cause clogging so that it can be printed over large areas, and thus is advantageous for mass production.
<56> Moreover, in the conductive ink composition according to the present invention, the mixing ratio of the copper (Cu) particles as the first metal particles to the silver (Ag) particles as the second metal particles may be 70:30 to 80:20. The conductive ink composition is inexpensive, because it comprises a significant amount of the conductive copper (Cu) particles that are significantly inexpensive compared to the silver (Ag) particles.
57> " Meanwhile, the copper (Cu) particles have a melting point of 1084.6 °C , and the silver (Ag) particles have a melting point of 961 V . However, when the copper (Cu) particles and the silver (Ag) particles are mixed at a ratio of 70:30 to 80:20, the metal particle mixture will have a melting point of about 779 °C , which is lower than the melting point of each of the metal particles before mixing. This low melting point is defined as eutectic point. In other words, the conductive ink composition according to the present invention can be fired at a low temperature of 150 to 200 °C by virtue of the eutectic point resulting from the specific mixing ratio between
the copper (Cu) particles and the silver (Ag) particles. Despite firing at this low temperature, the electrode formed from the conductive ink composition can have high electrical conductivity.
<58> FIG. 3 is a scanning electron microscope (SEM) photograph of the conductive ink composition according to the present invention before firing it, and FIG. 4 is a scanning electron microscope (SEM) photograph of the inventive conductive ink composition after firing at low temperature. As can be seen in FIG. 4, in the conductive ink composition according to the present invention, nano-sized silver (Ag) particles are interposed between submicron- sized copper (Cu) particles to form bridges therebetween, and furthermore, a low eutectic point is achieved by the specific mixing ratio between the copper (Cu) particles and the silver (Ag) particles, suggesting that the metal particles contained in the composition can be sintered even when they are fired even at low temperature.
<59> The conductive ink composition according to the present invention may further comprise a suitable binder in order to ensure the uniform dispersion of the first metal particles and the second metal particles, the excellent printability of the composition by control of the viscosity and thixotropic index thereof, and the close adhesion of an electrode to a flexible substrate made of a material such as polyimide or polyester in a process of applying the composition to the flexible substrate to form the electrode.
<60> The binder is not specifically limited and may be, for example, cellulose-based resin such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose or nitrocellulose, polyvinyl chloride resin or its copolymer, polyvinyl alcohol resin, polyvinyl pyrrol idone resin, acrylic resin such as polymethylmethacrylate, a vinyl acetate-acrylic acid ester copolymer resin, butyral resin such as polyvinyl butyral, alkyd resin such as phenol modified alkyd resin or castor oil fatty acid modified alkyd resin, epoxy resin, phenol resin, rosin ester resin, polyester resin, or a combination of two or more thereof. The binder that is used in the present invention is preferably polyester resin having high viscosity in order to ensure the excellent printability of the inventive conductive ink composition
by control of the viscosity and thixotropic index thereof.
<6i> The content of the binder may be 2-10 parts by weight based on 100 parts by weight of the conductive metal particles contained in the inventive conductive ink composition. If the content of the binder is less than 2 parts by weight, the viscosity of the conductive ink composition will be excessively reduced, making it difficult to prepare a paste-type composition for screen printing, and if the content of the binder is more than 10 parts by weight, the viscosity and thixotropic index of the conductive ink composition will be excessively increased, resulting in an increase in the linear resistance of the electrode formed and a decrease in the electrical conduct ivity.
<62> The conductive ink composition according to the present invention may further comprise a suitable organic solvent in order to ensure the uniform dispersion of the first and second metal particles, the excellent printability of the composition by control of the viscosity and thixotropic index thereof, and the processabi 1 ity and workability of the composition in the electrode forming process.
<63> The organic solvent is not specifically limited, and examples thereof
. include hydrocarbon solvents, such as hexane, cyclohexane, and toluene; chlorinated hydrocarbon solvents, such as dichloroethylene, dichloroethane, and dichlorobenzene! cyclic ether solvents, such as tetrahydrofuran, furan, tetrahydropyran, pyran, dioxane, 1,3-dioxolane, and trioxane! an amide solvent, such as Ν,Ν-dimethylformamide, and Ν,Ν-dimethylacetamide; sulfoxide solvents, .such as dimethylsulfoxide, and diethylsulfoxide; ketone solvents, such as acetone, methyl ethyl ketone, diethylketone, and cyclohexanone; alcohol or polyhydric alcohol solvents, such as ethanol, 2-propanol, 1- butanol, diacetone alcohol, and glycol; acetate solvents, such as butyl acetate, 2,2,4-tr imethyl-l,3-pentanediol monoacetate, 2,2,4-tr imethyl-1, 3- pentanediol monopropionate, 2,2,4-tr imethyl-l,3-pentanediol monobutyrate, 2,2,4-trimethyl-l,3-pentanediol monoisobutyrate (Texanol), 2,2,4-tr iethyl- 1,3-pentanediol monoacetate, ethylene glycol monobutyl ether acetate, and diethylene glycol monobutyl ether acetate; polyhydric alcohol ether solvents,
such as butyl cellosolve, and diethylene glycol diethyl ether; terpene- solvents, such as a-terpinene, a-terpineol, myrcene, al lo-ocimene, limonene, dipentene, a-pinene, β-pinene, terpineol, carvone, ocimene, and phel landrene; and mixtures thereof.
<64> The organic solvent that is used in the present invention includes a high-boiling-point organic solvent such as a-terpineol (boiling point: 219 °C). If the boiling point of the organic solvent during firing in the electrode forming process is low, the organic solvent will be rapidly volatilized so that it is removed before sintering of the conductive metal particles contained in the applied conductive ink composition, and thus an electrode cannot be formed from the composition. Preferably, the organic solvent may include a combination of a-terpinene and butyl acetate at a ratio of 5:5 to 8:2 in order to ensure processabi lity and workability in the electrode forming process, as well as the excellent printability of the inventive conductive ink composition by control of the viscosity and thixotropic index thereof.
<65> The content of the organic solvent may be 5-20 parts by weight based on
100 parts by weight of the conductive metal particles contained in the conductive ink composition of the present invention. If the content of the organic solvent is less than 5 parts by weight, it will be difficult to prepare a paste type composition for screen printing, and if the content of the organic solvent is more than 20 parts by weight, the thixotropic index of the conductive ink composition will be excessively reduced to cause spreading after printing, suggesting that the composition has poor printability.
;66> The conductive ink composition according to the present invention may further comprise a phosphorus-containing compound, a flux or other additives. The phosphorus-containing compound and the flux can further increase the oxidation resistance of the conductive ink composition of the conductive ink composition and the electrical conductivity of the electrode formed. Examples of the phosphorus-containing compound include phosphorus-based inorganic acids such as phosphoric acid; phosphates such as ammonium phosphate*, phosphoric acid esters such as phosphoric acid alkyl ester or
phosphoric acid aryl ester; cyclic phosphazenes such as hexaphenoxyphosphazene ; or derivatives thereof. The content of the phosphorus-containing compound may be 0.5-10 parts by weight based on the total weight of the conductive ink composition.
<67> Examples of the flux include fatty acids, boronic acid compounds, fluoride compounds, and borofluoride compounds, for example, lauric acid, myristic acid, palmitic acid, stearic acid, sorbic acid, stearolic acid, boron oxide, potassium borate, sodium borate, lithium borate, potassium borofluoride, sodium borofluoride, lithium borofluoride, acidic potassium fluoride, acidic sodium fluoride, acidic lithium fluoride, potassium fluoride, sodium fluoride, lithium fluoride, etc. The content of the flux may be 0.1-5 parts by weight based on the total weight of the conductive ink composition.
<68> Examples of the other additives include plast icizers, dispersing agents, surfactants, inorganic binders, metal oxides, ceramic materials, organic metal compounds, etc.
<69> The conductive ink composition according to the present invention can be prepared by any method. For example, it can be prepared by dispersing and mixing the first metal particles, the second metal particles, the binder and the organic solvent, optionally the phosphorus-containing compound, the flux and other additives, using conventional dispersing and mixing methods.
<70> The conductive ink composition according to the present invention preferably has a thixotropic index of 4-6 depending on the kind of conductive metal particles, binder, organic solvent and the like therein and the mixing ratio therebetween.
7i> Generally, when the inventive conductive ink composition having a thixotropic index of 4-6 is screen-printed once on a flexible substrate made of a material such as polyimide or polyester, and then is fired at a temperature of 200 °C or lower for about 30 minutes, an electrode having a
-5
thickness of 10-25 and a linear resistance of 4X10 Ω · cm can be formed.
In another aspect, the present invention is directed to a method of forming an electrode in a liquid crystal display (LCD), a plasma display
panel (PDP), an organic transistor, a smart card, an antenna, a cell, a fuel cell, a sensor, a touch screen, a printed circuit board (PCB), particularly a flexible printed circuit board (FPCB), etc., by screen printing using the conductive ink composition of the present invention.
<73> Specifically, the inventive method for forming an electrode comprises the steps of: i) placing in a screen printing frame a base substrate in which the electrode is to be formed; ii) placing on the base substrate a silk, nylon, polyester or metal screen having open areas formed according to the pattern of the electrode to be formed; iii) forcing the conductive ink composition of the present invention through the open areas of the screen with a squeegee to apply the conductive ink composition to the base substrate according to the electrode pattern; and iv) drying and firing the conductive ink composition, applied to the base substrate, at a temperature of 150 to 200 °C for 30-60 minutes, thereby forming the electrode.
<74> Herein, the base substrate may be a base substrate which is used in a liquid crystal display (LCD), a plasma display panel (PDP), an organic transistor, a smart card, an antenna, a cell, a fuel cell, a touch screen, a printed circuit board (PCB), particularly a flexible printed circuit board (FPCB), etc.
<75> Preferably, the electrode formed as described above may have a
-5
thickness of 10-25 m and a linear resistance of 4x10 Ω · cm or less.
<76> Exam les
<77> Hereinafter, the present invention will be described in further detail with reference to examples. However, the present invention is not limited to the examples described herein and may also be embodied in other forms. Rather, the examples disclosed herein are provided to enable the disclosure of the present invention to be thoroughly and completely understood and the idea of the present invention to be sufficiently delivered to those skilled in the art .
78> 1. Preparation Examples
79> According to the components and contents shown in Table 1 below, submicron-sized copper (Cu) particles, nano-sized silver (Ag) particles, a
.
binder and an organic solvent were mixed with each other at the ratio shown in Table 1 and were then dispersed using a PD mixer (manufactured by Nanointech, Korea) for about 30 minutes. The dispersed ink composition was stirred so as to be highly dispersed using a 3-roll mill (C-4, Inoue, Japan) for about 30 minutes. Finally, the dispersed composition was filtered to remove foreign matter, thereby preparing conductive ink compositions of Examples and Comparative Examples. In Table 1 below, the amounts of the components are parts by weight.
<80> iTable 1]
- Copper (Cu) particles (manufactured by Nano Technology Research
Association, Korea; product name: Cu powder (prepared by an electrical explosion method and having a mean diameter (D50) of 365 nm)
<82> - Silver (Ag) particles (manufactured by LS Cable & System, Korea; product name: silver nanopart icles (prepared by a wet reduction method and capped with oleic acid)
<83> - Binder: polyester (manufactured by Birdchem; product name: AD302)
<84> - Organic solvent: 5:5 mixture of a-terpineol (manufactured by Samchun
Chemical, Korea) and butylacetate (manufactured by Daejung Chemicals &
Metals, Korea).
:85> 2. Evaluation method and results
-86> The conductive ink composition prepared in each of the Examples and the
Comparative Examples was screen-printed on a polyimide substrate to form an applied portion having a size of 1 cm (width) x 10 cm (length), and was then fired (dried) at 200 °C in an air atmosphere for 30 minutes. The linear resistance and thixotropic index of the dried or fired printed electrode were measured, and the results of the measurement are shown in Table 2 below.
[Table 2]
As can be seen in Table 2 above, although the conductive ink compositions of Examples 1 and 2 were fired at a low temperature of 200 °C , the nano-sized silver (Ag) particles were interposed between the submicron- sized copper (Cu) particles in the composition to form bridges therebetween. Also, as shown in FIG. 4, the metal particles were easily sintered due to a low eutectic point resulting from the specific mixing ratio of the copper (Cu) particles to the silver (Ag) particles. In addition, the electrodes formed from the conductive ink compositions had a thixotropic index of 4.5 or
-5
4.8, a thickness of 20 p , and a low linear resistance of 4X10 Ω · cm or less, indicating high electrical conductivity.
9i> However, in the case of the . conduct ive ink composition of Comparative
Example 1 containing submicron-sized copper (Cu) particles without containing nano-sized silver (Ag) particles and the conductive ink composition of Comparative Example 2 containing a very small amount of nano-sized silver (Ag) particles, the formation of bridges between the copper (Cu) particles by the nano-sized silver (Ag) particles did not occur or was insufficient, and the low eutectic point of the particle mixture could not be achieved. Thus, when the conductive ink compositions of the Comparative Examples were fired at a low temperature of 200 °C , sintering of the metal particles did not substantially occur, and the resulting electrodes had a linear resistance
-5
much higher than 4X10 Ω · cm, indicating low electrical conductivity.
;92> Although the preferred embodiments of the present invention have been described for illustrative purposes, those skilled in the art will appreciate
that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims
[Claim 1]
<95> A conductive ink composition comprising:
<96> conductive metal particles including submicron-sized copper (Cu) particles and nano-sized silver (Ag) particles at a ratio of copper (Cu): silver (Ag)=70:30 to 80:20; and
<97> based on 100 parts by weight of the conductive metal particles,
2-10 parts by weight of a binder and 5-20 parts by weight of an organic solvent. [Claim 2]
<98> The conductive ink composition of claim 1, wherein the submicron-sized copper (Cu) particles, which have a median weight in the particle size distribution based on the copper (Cu) particles' weights, have a mean diameter (D50) of 350-380 nm, and the nano-sized silver (Ag) particles, which have a median weight in the particle size distribution based on the silver (Ag) particles' weights, have a mean diameter (D50) of 100 nm or smaller.
[Claim 3]
<99> The conductive ink composition of claim 1 or 2, wherein the copper (Cu) particles are surface-treated with at least one surface treatment agent selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organic metal compound salts, polyani 1 ine-based resins, and metal alkoxides.
[Claim 4]
-ioo> The conductive ink composition of claim 1 or 2, wherein the copper (Cu) particles have a spherical shape, a flat shape or a plate shape.
[Claim 5]
ioi> The conductive ink composition of claim 1 or 2, wherein the binder is selected from the group consisting of cellulose-based resin, polyvinyl chloride resin or its copolymer, polyvinyl alcohol-based resin, polyvinyl pyrrol idone-based resin, acrylic resin, a vinyl acetate-acrylic acid ester copolymer, butyral resin, alkyd resin, epoxy resin, phenol resin, rosin ester resin, polyester resin, and a mixture of two or more thereof.
[Claim 6]
i02> The conductive ink composition of claim 1 or 2, wherein the organic solvent is selected from the group consisting of hydrocarbon solvents, chlorinated hydrocarbon solvents, cyclic ether solvents, amide solvents, ketone solvents, alcohol or polyhydric alcohol solvents, acetate solvents, polyhydric alcohol ether solvents, terpene solvents, and a mixture of two or more thereof.
[Claim 7]
i03> The conductive ink composition of claim 1 or 2, wherein the binder is polyester resin, and the organic solvent is a 5:5 to 8:2 mixture of a- terpineol and butyl acetate.
[Claim 8]
i04> The conductive ink composition of claim 1 or 2, wherein the composition further comprises a phosphorus-containing compound, a flux, a plasticizer, a dispersing agent, a surfactant, an inorganic binder, a metal oxide, a ceramic material, an organic metal compound, or a mixture of two or more thereof.
[Claim 9]
i05> The conductive ink composition of claim 1 or 2, wherein the composition has a thixotropic index of 4-6.
[Claim 10]
i06> A method for forming an electrode, the method comprising the steps of: i 7> placing in a screen printing frame a base substrate in which the electrode is to be formed;
i08> placing on the base substrate a silk, nylon, polyester or metal screen having open areas formed according to the pattern of the electrode to be formed;
i09> forcing the conductive ink composition of claim 1 or 2 through the open areas of the screen with a squeegee to apply the conductive ink composition to the base substrate according to the electrode pattern; and
iio> drying and firing the conductive ink composition, applied to the base substrate, at a temperature of 150 to 200 °C for 30-60 minutes, thereby forming the electrode.
[Claim 11]
The method of claim 10, wherein the formed electrode has a thickness of
-5
and a linear resistance of 4X10 Ω ■ cm or less.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130006327A KR20140094690A (en) | 2013-01-21 | 2013-01-21 | Electroconductive ink comoposition and method for forming an electrode by using the same |
| KR10-2013-0006327 | 2013-01-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2014112683A1 true WO2014112683A1 (en) | 2014-07-24 |
Family
ID=51209765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2013/001997 WO2014112683A1 (en) | 2013-01-21 | 2013-03-13 | Conductive ink composition and method for forming electrode using the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR20140094690A (en) |
| WO (1) | WO2014112683A1 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018051830A1 (en) * | 2016-09-16 | 2018-03-22 | 株式会社ノリタケカンパニーリミテド | Silver paste for flexible substrate |
| WO2018134411A1 (en) | 2017-01-23 | 2018-07-26 | Francisco Albero S.A.U. | Stretchable conductive ink |
| EP3244420A4 (en) * | 2015-01-13 | 2018-08-22 | Dowa Electronics Materials Co., Ltd. | Electroconductive paste and method for manufacturing electroconductive film using same |
| EP3354698A4 (en) * | 2015-10-26 | 2019-05-15 | Korea Research Institute of Chemical Technology | Ink composition for photonic sintering and method for producing same |
| WO2019098196A1 (en) * | 2017-11-14 | 2019-05-23 | 日立化成株式会社 | Composition, conductor, method for manufacturing same, and structure |
| US10403821B2 (en) | 2014-05-22 | 2019-09-03 | Cambridge Display Technology Limited | Method of making an electrode |
| CN111525264A (en) * | 2020-05-21 | 2020-08-11 | 信利(仁寿)高端显示科技有限公司 | Liquid crystal antenna |
| EP3808826A4 (en) * | 2018-06-12 | 2022-03-16 | DIC Corporation | Highly electrically conductive silver ink composition and wiring obtained using same |
| CN114867797A (en) * | 2019-12-11 | 2022-08-05 | 吉尼斯油墨公司 | Ink based on silver nanoparticles |
| EP4078624A4 (en) * | 2019-12-20 | 2023-10-18 | Henkel AG & Co. KGaA | Silver sintering composition containing copper alloy for metal bonding |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6404614B2 (en) * | 2014-06-25 | 2018-10-10 | 古河機械金属株式会社 | Manufacturing method of core-shell type metal fine particles, core-shell type metal fine particles, conductive ink and substrate |
| KR20170020630A (en) * | 2015-08-13 | 2017-02-23 | 주식회사 네패스 | Eco-friendly water-based conductive ink composition and conductive pen having the same |
| KR102283828B1 (en) * | 2017-09-28 | 2021-07-30 | 주식회사 소프트로닉스 | Method for manufacturing fiber based stretch sensor |
| KR102490064B1 (en) * | 2020-11-27 | 2023-01-19 | 한국전자기술연구원 | A Conductive Ink Composition and a Conductive Substrate using the same |
| GB202108059D0 (en) * | 2021-06-04 | 2021-07-21 | Qinetiq Ltd | A method of printing a component in an electrochemical cell |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005229106A (en) * | 2004-01-15 | 2005-08-25 | Ｎｅｘｔ Ｉ＆Ｄ株式会社 | Conductive material for drawing circuit |
| US20070131912A1 (en) * | 2005-07-08 | 2007-06-14 | Simone Davide L | Electrically conductive adhesives |
| US20100040846A1 (en) * | 2008-05-16 | 2010-02-18 | Bayer Materialscience Ag | Printable compositions containing silver nanoparticles, processes for producing electrically conductive coatings using the same, and coatings prepared thereby |
| KR20120110554A (en) * | 2011-03-29 | 2012-10-10 | 한국과학기술연구원 | Conductive ink composition, method for manufacturing the same and method for manufacturing conductive thin layer using the same |
-
2013
- 2013-01-21 KR KR1020130006327A patent/KR20140094690A/en not_active Application Discontinuation
- 2013-03-13 WO PCT/KR2013/001997 patent/WO2014112683A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005229106A (en) * | 2004-01-15 | 2005-08-25 | Ｎｅｘｔ Ｉ＆Ｄ株式会社 | Conductive material for drawing circuit |
| US20070131912A1 (en) * | 2005-07-08 | 2007-06-14 | Simone Davide L | Electrically conductive adhesives |
| US20100040846A1 (en) * | 2008-05-16 | 2010-02-18 | Bayer Materialscience Ag | Printable compositions containing silver nanoparticles, processes for producing electrically conductive coatings using the same, and coatings prepared thereby |
| KR20120110554A (en) * | 2011-03-29 | 2012-10-10 | 한국과학기술연구원 | Conductive ink composition, method for manufacturing the same and method for manufacturing conductive thin layer using the same |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10403821B2 (en) | 2014-05-22 | 2019-09-03 | Cambridge Display Technology Limited | Method of making an electrode |
| EP3244420A4 (en) * | 2015-01-13 | 2018-08-22 | Dowa Electronics Materials Co., Ltd. | Electroconductive paste and method for manufacturing electroconductive film using same |
| EP3354698A4 (en) * | 2015-10-26 | 2019-05-15 | Korea Research Institute of Chemical Technology | Ink composition for photonic sintering and method for producing same |
| US10822511B2 (en) | 2015-10-26 | 2020-11-03 | Korea Research Institute Of Chemical Technology | Ink composition for photonic sintering and method for producing same |
| WO2018051830A1 (en) * | 2016-09-16 | 2018-03-22 | 株式会社ノリタケカンパニーリミテド | Silver paste for flexible substrate |
| JPWO2018051830A1 (en) * | 2016-09-16 | 2019-07-04 | 株式会社ノリタケカンパニーリミテド | Silver paste for flexible substrates |
| WO2018134411A1 (en) | 2017-01-23 | 2018-07-26 | Francisco Albero S.A.U. | Stretchable conductive ink |
| WO2019098196A1 (en) * | 2017-11-14 | 2019-05-23 | 日立化成株式会社 | Composition, conductor, method for manufacturing same, and structure |
| CN111344814A (en) * | 2017-11-14 | 2020-06-26 | 日立化成株式会社 | Composition, conductor, method for producing same, and structure |
| JP7276140B2 (en) | 2017-11-14 | 2023-05-18 | 株式会社レゾナック | COMPOSITION, CONDUCTOR AND MANUFACTURING METHOD THEREOF, AND STRUCTURE |
| JPWO2019098196A1 (en) * | 2017-11-14 | 2020-11-19 | 昭和電工マテリアルズ株式会社 | Compositions, conductors and methods for their manufacture, and structures |
| CN111344814B (en) * | 2017-11-14 | 2021-11-16 | 昭和电工材料株式会社 | Composition, conductor, method for producing same, and structure |
| US11512214B2 (en) | 2017-11-14 | 2022-11-29 | Showa Denko Materials Co., Ltd. | Composition containing organic solvents with different vapor pressures, conductor made from composition, method for manufacturing conductor, and structure comprising conductor |
| EP3808826A4 (en) * | 2018-06-12 | 2022-03-16 | DIC Corporation | Highly electrically conductive silver ink composition and wiring obtained using same |
| CN114867797A (en) * | 2019-12-11 | 2022-08-05 | 吉尼斯油墨公司 | Ink based on silver nanoparticles |
| EP4078624A4 (en) * | 2019-12-20 | 2023-10-18 | Henkel AG & Co. KGaA | Silver sintering composition containing copper alloy for metal bonding |
| CN111525264A (en) * | 2020-05-21 | 2020-08-11 | 信利(仁寿)高端显示科技有限公司 | Liquid crystal antenna |
| CN111525264B (en) * | 2020-05-21 | 2022-01-18 | 信利(仁寿)高端显示科技有限公司 | Liquid crystal antenna |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140094690A (en) | 2014-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2014112683A1 (en) | Conductive ink composition and method for forming electrode using the same | |
| KR101207363B1 (en) | Composition for Conductive Paste Containing Nanometer-Thick Metal Microplates | |
| CN106573300B (en) | Silver powder, method for producing same, and conductive paste | |
| CN104303238B (en) | Transparent conductivity ink and transparent conductive patterns forming method | |
| KR20140098922A (en) | Electroconductive ink comoposition and method for forming an electrode by using the same | |
| US9067261B2 (en) | Process for making silver powder particles with very small size crystallites | |
| KR102236907B1 (en) | Silver-bismuth powder, conductive paste and conductive film | |
| KR20130050906A (en) | Low-temperature sintered silver nanoparticle composition and electronic articles formed using the same | |
| JP5866749B2 (en) | Conductive ink composition, method for producing electrically conductive portion, and use thereof | |
| US8715387B2 (en) | Process for making silver powder particles with small size crystallites | |
| WO2013077448A1 (en) | Conductive-pattern formation method and composition for forming conductive pattern via light exposure or microwave heating | |
| KR101796339B1 (en) | Electrically conductive copper particles, process for producing electrically conductive copper particles, composition for forming electrically conductive body, and base having electrically conductive body attached thereto | |
| CN105392583B (en) | Silver particles dispersion liquid | |
| WO2006074791A1 (en) | Printable medium for the etching of silicon dioxide and silicon nitride layers | |
| JP2012119611A (en) | Manufacturing method of through hole electrode substrate | |
| KR101273694B1 (en) | Copper nano paste and method for forming the copper nano paste, and method for forming electrode using the copper nano paste | |
| KR20120110554A (en) | Conductive ink composition, method for manufacturing the same and method for manufacturing conductive thin layer using the same | |
| TWI694469B (en) | Composition for forming conductive pattern and method of forming conductive pattern | |
| US8834957B2 (en) | Preparation method for an electroconductive patterned copper layer | |
| JP6562196B2 (en) | Copper fine particle sintered body and method for producing conductive substrate | |
| CN105788756B (en) | A kind of transparent metal conducting film and preparation method thereof | |
| JP5087384B2 (en) | Manufacturing method of conductive member and conductive member | |
| US20120220072A1 (en) | Copper nano paste, method for forming the copper nano paste, and method for forming electrode using the copper nano paste | |
| CN104599740B (en) | Conductive silver paste with nanocarbon | |
| DE112014006903T5 (en) | Solar cells with copper electrodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13871819 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 13871819 Country of ref document: EP Kind code of ref document: A1 |