JP6240528B2 - Nickel ink composition - Google Patents
Nickel ink composition Download PDFInfo
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- JP6240528B2 JP6240528B2 JP2014028367A JP2014028367A JP6240528B2 JP 6240528 B2 JP6240528 B2 JP 6240528B2 JP 2014028367 A JP2014028367 A JP 2014028367A JP 2014028367 A JP2014028367 A JP 2014028367A JP 6240528 B2 JP6240528 B2 JP 6240528B2
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- JP
- Japan
- Prior art keywords
- nickel
- ink composition
- composition according
- formate
- metal film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 209
- 229910052759 nickel Inorganic materials 0.000 title claims description 101
- 239000000203 mixture Substances 0.000 title claims description 82
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 18
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 13
- 150000002169 ethanolamines Chemical class 0.000 claims description 11
- -1 triethylenetetramine nickel formic acid Chemical compound 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims description 4
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 4
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 4
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- LSYBWANTZYUTGJ-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl-methylamino]ethanol Chemical compound CN(C)CCN(C)CCO LSYBWANTZYUTGJ-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 5
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000843 powder Substances 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- VKABKQBHBBROCU-UHFFFAOYSA-N 2-(2,2,3-trimethylpiperazin-1-yl)ethanamine Chemical compound CC1NCCN(CCN)C1(C)C VKABKQBHBBROCU-UHFFFAOYSA-N 0.000 description 2
- QHTUMQYGZQYEOZ-UHFFFAOYSA-N 2-(4-methylpiperazin-1-yl)ethanol Chemical compound CN1CCN(CCO)CC1 QHTUMQYGZQYEOZ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012971 dimethylpiperazine Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- 101100063069 Caenorhabditis elegans deg-1 gene Proteins 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- SMAMDWMLHWVJQM-UHFFFAOYSA-L nickel(2+);diformate;dihydrate Chemical compound O.O.[Ni+2].[O-]C=O.[O-]C=O SMAMDWMLHWVJQM-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Description
本発明はニッケルインク組成物に関する。さらに詳しくは、塗布又は印刷した後、加熱することによりニッケル金属膜を形成するためのニッケルインク組成物に関するものである。 The present invention relates to a nickel ink composition. More specifically, the present invention relates to a nickel ink composition for forming a nickel metal film by heating after coating or printing.
従来、基板、電子部品などに電極、配線を形成する方法として、基板、電子部品に金属をメッキした後、これをフォトレジストなどでマスクし、マスクしていない金属をエッチング除去する方法が広く使用されてきた。しかし、この方法は、高導電性の微細配線を形成するには好適だが、工程数が多く、金属資源を無駄にするという問題がある。 Conventionally, as a method of forming electrodes and wiring on a substrate, electronic parts, etc., after plating a metal on the substrate, electronic parts, masking it with a photoresist, etc., and etching away the unmasked metal is widely used. It has been. However, this method is suitable for forming highly conductive fine wiring, but has a problem that the number of processes is large and metal resources are wasted.
上記の方法以外にも、導電性インク組成物を基材に塗布又は印刷した後、加熱して電極又は電気配線等を形成するという方法も、広く用いられている。この方法は、工程数が少なく、金属資源も有効に使われる。金属としては、銀、アルミなどが実用化され、広く使用されている。これらのインク組成物の多くは、金属微粒子を使用しており、加熱で微粒子を凝集、融着させ、電極、配線を形成するものである。 In addition to the above method, a method of forming an electrode or an electric wiring by applying or printing a conductive ink composition on a substrate and then heating it is widely used. In this method, the number of processes is small, and metal resources are also effectively used. As metals, silver, aluminum and the like have been put into practical use and widely used. Many of these ink compositions use fine metal particles, and the fine particles are aggregated and fused by heating to form electrodes and wiring.
ニッケルインク組成物に関しても多くの開発がなされている。これらのニッケルインク組成物はニッケル金属粉末と有機バインダー、無機バインダー、溶剤から構成されている。例えば、ニッケル粉末、シランカップリング剤、溶剤からなるインク組成物（特許文献１、参照）、ニッケル粉末、樹脂結合剤、有機溶剤からなるインク組成物（特許文献２、参照）、ニッケル粉末、セラミック粉末からなるインク組成物（特許文献３、参照）、貴金属とニッケル塩から調製した平均一次粒子径が１００ｎｍ以下のニッケル微粒子を使用するインク組成物（特許文献４、参照）、酸化ニッケルとセラミック粉末の混合物を還元して得られたニッケル微粉末を使用するインク組成物（特許文献５、参照）、リンを含むニッケル粉末を使用するインク組成物（特許文献６、参照）、アルコール類、グリコール類にニッケル粒子を分散したインク組成物（特許文献７、参照）、ニッケル粉末、無機物、有機バインダー、溶剤からなるインク組成物（特許文献８、参照）、ニッケル塩、アミンを還元剤で還元して得られたニッケルコロイドを使用するインク組成物（特許文献９、参照）、塩基性炭酸ニッケルをヒドラジンで還元して得られたニッケル粉末を使用する方法（特許文献１０、参照）などが知られている。 Many developments have also been made on nickel ink compositions. These nickel ink compositions are composed of nickel metal powder, an organic binder, an inorganic binder, and a solvent. For example, an ink composition comprising nickel powder, a silane coupling agent and a solvent (see Patent Document 1), an ink composition comprising nickel powder, a resin binder and an organic solvent (see Patent Document 2), nickel powder, ceramic Ink composition comprising powder (see Patent Document 3), ink composition using nickel fine particles having an average primary particle diameter of 100 nm or less prepared from noble metal and nickel salt (see Patent Document 4), nickel oxide and ceramic powder Ink composition using nickel fine powder obtained by reducing the mixture of the above (Patent Document 5, see), Ink composition using nickel powder containing phosphorus (see Patent Document 6,), alcohols, glycols An ink composition in which nickel particles are dispersed (see Patent Document 7), nickel powder, an inorganic substance, an organic binder, and a solvent. Ink composition (see Patent Document 8), nickel salt, ink composition using nickel colloid obtained by reducing amine with reducing agent (see Patent Document 9), basic nickel carbonate reduced with hydrazine A method of using the nickel powder obtained in this way (see Patent Document 10) is known.
しかし、これらのインク組成物は、いずれもニッケル粒子を含んでおり、近年の印刷の微細化に関しては問題がある。安価なニッケル粉末は粒径が大きいため、微細印刷に適しておらず、微細印刷に適するようニッケル粒子を微細化すると高価になる。 However, all of these ink compositions contain nickel particles, and there is a problem with the recent miniaturization of printing. Since inexpensive nickel powder has a large particle size, it is not suitable for fine printing, and it becomes expensive if the nickel particles are made fine so as to be suitable for fine printing.
そこで、ニッケル粒子を含まないインク組成物の開発が望まれている。 Therefore, development of an ink composition that does not contain nickel particles is desired.
また、バインダーを含むニッケルインク組成物は導電性が低い。導電性を高めるには、インク組成物を塗布した後、３００℃以上の高温で処理する必要があり、適用できる用途に制限があった。 Moreover, the nickel ink composition containing a binder has low electrical conductivity. In order to increase the electrical conductivity, it is necessary to treat at a high temperature of 300 ° C. or higher after applying the ink composition, and there is a limit to the applications that can be applied.
本発明は上記の課題に鑑みてなされたものであり、その目的は、ニッケル粒子を含まず、３００℃以下の温度で焼成することができる、高導電性（低抵抗）のニッケルインク組成物を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a highly conductive (low resistance) nickel ink composition that does not contain nickel particles and can be fired at a temperature of 300 ° C. or lower. It is to provide.
本発明者は、ニッケル金属膜を形成するインク組成物について鋭意検討した結果、ギ酸ニッケル（ＩＩ）、エチレンアミン類を含むインク組成物が、窒素下２００℃で焼成してもニッケル金属膜が形成でき、しかもその膜が高導電性（低抵抗）となるという新規な事実を見出し、本発明を完成させるに至った。 As a result of intensive studies on an ink composition for forming a nickel metal film, the present inventor has formed a nickel metal film even when an ink composition containing nickel (II) formate and ethyleneamines is baked at 200 ° C. under nitrogen. In addition, the inventors have found a novel fact that the film has high conductivity (low resistance), and completed the present invention.
すなわち、本発明は、以下に示すとおりのニッケルインク組成物である。 That is, the present invention is a nickel ink composition as shown below.
［１］ギ酸ニッケル（ＩＩ）及びエチレンアミン類を含むニッケルインク組成物。 [1] A nickel ink composition comprising nickel (II) formate and ethyleneamines.
［２］エチレンアミン類が、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ピペラジン、アミノエチルピペラジン、テトラメチルエチレンジアミン、ペンタメチルジエチレントリアミン、ジメチルピペラジン、トリメチルアミノエチルピペラジンから成る群より選ばれる少なくとも一種である上記［１］に記載のニッケルインク組成物。 [2] At least one selected from the group consisting of ethylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine, aminoethylpiperazine, tetramethylethylenediamine, pentamethyldiethylenetriamine, dimethylpiperazine, and trimethylaminoethylpiperazine The nickel ink composition as described in [1] above.
［３］エチレンアミン類が、トリエチレンテトラミンである上記［１］又は［２］に記載のニッケルインク組成物。 [3] The nickel ink composition according to [1] or [2], wherein the ethyleneamine is triethylenetetramine.
［４］ギ酸ニッケル（ＩＩ）とトリエチレンテトラミンのモル比が１：１〜１：６である上記［３］に記載のニッケルインク組成物。 [4] The nickel ink composition according to the above [3], wherein the molar ratio of nickel (II) formate and triethylenetetramine is 1: 1 to 1: 6.
［５］加熱しニッケル金属膜を形成する際、酸素濃度１０％以下で実施する上記［１］〜［４］に記載のニッケルインク組成物。 [5] The nickel ink composition according to the above [1] to [4], wherein the nickel metal film is formed by heating at an oxygen concentration of 10% or less.
［６］基板に塗布後、温度１９０℃以上で加熱しニッケル金属膜を形成する上記［１］〜［５］のいずれかに記載のニッケルインク組成物。 [6] The nickel ink composition according to any one of the above [1] to [5], wherein the nickel metal film is formed by applying a nickel metal film after being applied to a substrate at a temperature of 190 ° C or higher.
［７］エチレンアミン類が、エチレンジアミンである上記［１］又は［２］に記載のニッケルインク組成物。 [7] The nickel ink composition according to [1] or [2], wherein the ethyleneamine is ethylenediamine.
［８］さらにエタノールアミン類を含む上記［１］、［２］又は［７］のいずれかに記載のニッケルインク組成物。 [8] The nickel ink composition according to any one of [1], [2] or [7], further comprising ethanolamines.
［９］エタノールアミン類が、モノエタノールアミン、Ｎ−メチルエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ−メチルジエタノールアミン、アミノエチルエタノールアミン、Ｎ，Ｎ，Ｎ’−トリメチルアミノエチルエタノールアミン、Ｎ−（２−ヒドロキシエチル）モルホリン、Ｎ−（２−ヒドロキシエチル）ピペラジン、Ｎ−メチル−Ｎ’−（２−ヒドロキシエチル）ピペラジンから成る群より選ばれる少なくとも一種である上記［８］に記載のニッケルインク組成物。 [9] Ethanolamines are monoethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, aminoethylethanolamine, N, N, N′-trimethyl The above is at least one selected from the group consisting of aminoethylethanolamine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxyethyl) piperazine, N-methyl-N ′-(2-hydroxyethyl) piperazine The nickel ink composition according to [8].
［１０］エチレンアミン類が、ギ酸ニッケル（ＩＩ）に対し、モル比で０．５〜１０である上記［１］、［２］、［７］〜［９］のいずれかに記載のニッケルインク組成物。 [10] The nickel ink according to any one of [1], [2], and [7] to [9], wherein the ethyleneamine is 0.5 to 10 in molar ratio with respect to nickel (II) formate. Composition.
［１１］エタノールアミン類が、ギ酸ニッケル（ＩＩ）に対し、モル比で１以上である上記［８］〜［１０］のいずれかに記載のニッケルインク組成物。 [11] The nickel ink composition according to any one of [8] to [10], wherein the ethanolamine is 1 or more in molar ratio with respect to nickel (II) formate.
［１２］さらに、有機溶媒を含む上記［１］、［２］、［７］〜［１１］のいずれかに記載のニッケルインク組成物。 [12] The nickel ink composition according to any one of [1], [2], and [7] to [11], further including an organic solvent.
［１３］有機溶媒が、アルコール、エーテル、ケトン、アミド、エステルから成る群より選ばれる少なくとも一種である上記［１２］に記載のニッケルインク組成物。 [13] The nickel ink composition according to [12], wherein the organic solvent is at least one selected from the group consisting of alcohol, ether, ketone, amide, and ester.
［１４］基板に塗布後、温度１５０℃以上で加熱しニッケル金属膜を形成する上記［１］、［２］、［７］〜［１３］のいずれかに記載のニッケルインク組成物。 [14] The nickel ink composition according to any one of the above [1], [2], and [7] to [13], wherein the nickel metal film is formed by applying to a substrate and then heating at a temperature of 150 ° C. or higher.
本発明のニッケルインク組成物は、ニッケル粒子を含まず高導電性（低抵抗）のニッケル金属膜が得られるニッケルインク組成物であり、コンデンサなどの電子デバイスの製造において、少ない工程で配線が形成でき、しかも低温で微細配線を形成できるため、工業的に極めて有用である。 The nickel ink composition of the present invention is a nickel ink composition that does not contain nickel particles and can provide a highly conductive (low resistance) nickel metal film. In the manufacture of electronic devices such as capacitors, wiring is formed in a small number of steps. In addition, since fine wiring can be formed at a low temperature, it is extremely useful industrially.
本発明のニッケルインク組成物の必須成分は、ギ酸ニッケル（ＩＩ）、エチレンアミン類である。 The essential components of the nickel ink composition of the present invention are nickel formate (II) and ethyleneamines.
本発明のニッケルインク組成物において、ギ酸ニッケル（ＩＩ）は、加熱によってニッケル金属を生成する。使用するギ酸ニッケル（ＩＩ）に特に制限はなく、工業的に一般に流通しているものを使用することができる。ギ酸ニッケル（ＩＩ）は無水塩を使用しても良いし、水和塩を使用しても良い。 In the nickel ink composition of the present invention, nickel (II) formate generates nickel metal by heating. There is no restriction | limiting in particular in nickel (II) formate to use, What is generally distribute | circulated industrially can be used. Nickel formate (II) may be an anhydrous salt or a hydrated salt.
本発明のニッケルインク組成物において、エチレンアミン類とは、エチレン鎖の両端にアミノ基を有する化合物をいう。エチレンアミン類は、ギ酸ニッケル（ＩＩ）を低温で分解するために使用する。 In the nickel ink composition of the present invention, ethyleneamines refer to compounds having amino groups at both ends of the ethylene chain. Ethyleneamines are used to decompose nickel (II) formate at low temperatures.
本発明のニッケルインク組成物において、エチレンアミン類を例示すると、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ピペラジン、アミノエチルピペラジン、テトラメチルエチレンジアミン、ペンタメチルジエチレントリアミン、ジメチルピペラジン、トリメチルアミノエチルピペラジン等が挙げられる。これらのエチレンアミン類のいずれを使用しても良く、ニッケル金属膜の形成が容易なトリエチレンテトラミン、ニッケル膜形成後に残存し難く、ギ酸ニッケル（ＩＩ）を溶解し易いエチレンジアミンが特に好ましい。これらのエチレンアミンは単独で使用しても、二種類以上を使用しても良い。 Examples of ethyleneamines in the nickel ink composition of the present invention include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine, aminoethylpiperazine, tetramethylethylenediamine, pentamethyldiethylenetriamine, dimethylpiperazine, trimethylaminoethylpiperazine. Etc. Any of these ethyleneamines may be used, and triethylenetetramine, which is easy to form a nickel metal film, and ethylenediamine, which hardly remains after the nickel film is formed and easily dissolves nickel (II) formate, are particularly preferable. These ethyleneamines may be used alone or in combination of two or more.
本発明のニッケルインク組成物において、好ましく用いられるトリエチレンテトラミンとギ酸ニッケル（ＩＩ）を含む組成物は、室温で安定であり、加熱した場合は１９０℃で容易に分解する。トリエチレンテトラミンは加熱時に揮発し、ニッケル金属膜に残存しない。使用するトリエチレンテトラミンに特に制限はなく、工業的に広く流通している安価な製品を使用することができる。一般にトリエチレントトラミンとして知られている工業製品は、直鎖状トリエチレンテトラミン、分岐状トリエチレンテトラミン、２種類のピペラジン誘導体を主成分とする４種以上のアミン混合物であり、混合物を使用しても一向に差支えない。 In the nickel ink composition of the present invention, a composition containing triethylenetetramine and nickel (II) formate that is preferably used is stable at room temperature and easily decomposes at 190 ° C. when heated. Triethylenetetramine volatilizes during heating and does not remain in the nickel metal film. There is no restriction | limiting in particular in the triethylenetetramine to be used, The cheap product currently distribute | circulated widely industrially can be used. The industrial product generally known as triethylenetotolamine is a mixture of four or more amines based on linear triethylenetetramine, branched triethylenetetramine, and two kinds of piperazine derivatives. But it doesn't matter.
本発明のニッケルインク組成物において、トリエチレンテトラミン以外のアミンを添加することができる。添加できるアミンとしては、オクチルアミン、１−アミノデカン、ドデシルアミン、テトラデシルアミン、ヘキサデシルアミン、オレイルアミンなどが例示できるが、これ以外のアミンを添加しても一向に差支えない。 In the nickel ink composition of the present invention, an amine other than triethylenetetramine can be added. Examples of the amine that can be added include octylamine, 1-aminodecane, dodecylamine, tetradecylamine, hexadecylamine, oleylamine, and the like.
本発明のニッケルインク組成物において、ギ酸ニッケル（ＩＩ）とトリエチレンテトラミンの比は、得られるニッケル金属膜の導電性及び膜厚の観点から、モル比で、１：１〜１：６が好ましく、１：１〜１：４がさらに好ましい。 In the nickel ink composition of the present invention, the ratio of nickel (II) formate to triethylenetetramine is preferably 1: 1 to 1: 6 in terms of molar ratio from the viewpoint of the conductivity and film thickness of the resulting nickel metal film. 1: 1 to 1: 4 are more preferable.
本発明のニッケルインク組成物には、防食剤、溶剤、増粘剤、界面活性剤も添加することができる。これらの添加剤には一般に使用されているものを使用することができ、特に制限はない。防食剤は、ニッケル膜、ニッケル配線を形成した後、ニッケル金属を保護するのに有効であり、溶剤、増粘剤、界面活性剤は、インクの塗布性、安定性を改良できる。 An anticorrosive, a solvent, a thickener, and a surfactant can also be added to the nickel ink composition of the present invention. As these additives, those commonly used can be used, and there is no particular limitation. The anticorrosive is effective for protecting the nickel metal after forming the nickel film and the nickel wiring, and the solvent, the thickener and the surfactant can improve the coating property and stability of the ink.
本発明のニッケルインク組成物において、好ましく用いられるエチレンジアミンとギ酸ニッケル（ＩＩ）を含む組成物を使用する場合は、さらにエタノールアミン類を添加することが好ましい。 In the nickel ink composition of the present invention, when a composition containing ethylenediamine and nickel (II) formate, which are preferably used, is used, it is preferable to further add ethanolamines.
本発明のニッケルインク組成物において、エタノールアミン類とは、エチレン鎖にアミノ基と、水酸基が存在する化合物をいう。エタノールアミン類は、ギ酸ニッケル（ＩＩ）を溶解し、ニッケル塩の還元を促進するために添加する。またエタノールアミン類は空気中の炭酸ガスを吸収しても固体になりにくく、インクの物性が損なわれないし、空気中の酸素による金属、塩の酸化も抑制することができる。 In the nickel ink composition of the present invention, the ethanolamine refers to a compound in which an amino group and a hydroxyl group are present in an ethylene chain. Ethanolamines are added to dissolve nickel (II) formate and promote the reduction of the nickel salt. In addition, ethanolamines are difficult to become solid even when carbon dioxide in the air is absorbed, the physical properties of the ink are not impaired, and oxidation of metals and salts by oxygen in the air can be suppressed.
本発明のニッケルインク組成物において使用できるエタノールアミン類を例示すると、モノエタノールアミン、Ｎ−メチルエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ−メチルジエタノールアミン、アミノエチルエタノールアミン、Ｎ，Ｎ，Ｎ’−トリメチルアミノエチルエタノールアミン、Ｎ−（２−ヒドロキシエチル）モルホリン、Ｎ−（２−ヒドロキシエチル）ピペラジン、Ｎ−メチル−Ｎ’−（２−ヒドロキシエチル）ピペラジン等が挙げられる。これらのエタノールアミン類のいずれを使用しても良く、ニッケル膜形成後に残存し難く、しかも組成物の他の成分と反応し難い２−（ジメチルアミノ）エタノール、Ｎ−メチルジエタノールアミン、ギ酸ニッケル（ＩＩ）の溶解性に優れたモノエタノールアミンが特に好ましい。これらのエタノールアミン類は単独で使用しても、二種類以上を使用しても良い。 Examples of ethanolamines that can be used in the nickel ink composition of the present invention include monoethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, aminoethylethanolamine. N, N, N′-trimethylaminoethylethanolamine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxyethyl) piperazine, N-methyl-N ′-(2-hydroxyethyl) piperazine, etc. Can be mentioned. Any of these ethanolamines may be used, 2- (dimethylamino) ethanol, N-methyldiethanolamine, nickel formate (II) which does not easily remain after formation of the nickel film and does not easily react with other components of the composition. Monoethanolamine, which is excellent in solubility, is particularly preferred. These ethanolamines may be used alone or in combination of two or more.
本発明のニッケルインク組成物において、エチレンジアミンは、ギ酸ニッケル（ＩＩ）の溶解性及びエチレンジアミンの残存性の観点から、ギ酸ニッケル（ＩＩ）１モルに対して、モル比で０．５〜１０が好ましく、１〜８が更に好ましい。 In the nickel ink composition of the present invention, the ethylenediamine is preferably in a molar ratio of 0.5 to 10 moles with respect to 1 mole of nickel (II) formate, from the viewpoints of solubility of nickel formate (II) and residual ethylenediamine. 1 to 8 are more preferable.
本発明のニッケルインク組成物において、エタノールアミン類は、ギ酸ニッケル（ＩＩ）の溶解性、分散性の観点から、ギ酸ニッケル（ＩＩ）１モルに対して、モル比で１以上が好ましい。 In the nickel ink composition of the present invention, the ethanolamine is preferably in a molar ratio of 1 or more with respect to 1 mol of nickel (II) formate from the viewpoint of solubility and dispersibility of nickel (II) formate.
本発明のニッケルインク組成物には、有機溶媒を添加することができる。有機溶媒はインクを希釈するとともに、基材への親和性を高めることができる。使用できる有機溶媒に制限はなく、一般にインクに含まれているものが使用でき、あえて例示すると、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、オクタノール、シクロヘキサノール、ベンジルアルコール、フェノール、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、グリセリン、ターピネオールなどのアルコール、アセトン、メチルエチルケトン、メチルターシャリーブチルケトン、アセチルアセトン、アセトフェノンなどのケトン、ジエチルエーテル、テトラヒドロフラン、ジオキサン、エチレングリコールモノアルキルエーテル、エチレングリコールジアルキルエーテル、ジエチレングリコールモノアルキルエーテル、ジエチレングリコールジアルキルエーテル、プロピレングリコールモノアルキルエーテル、プロピレングリコールジアルキルエーテル、ジプロピレングリコールモノアルキルエーテル、ジプロピレングリコールジアルキルエーテルなどのエーテル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルホルムアミド、アセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドンなどのアミド、ギ酸メチル、ギ酸エチル、酢酸エチル、炭酸ジメチル、炭酸エチレン、炭酸プロピレンなどのエステルなどが挙げられる。 An organic solvent can be added to the nickel ink composition of the present invention. The organic solvent can dilute the ink and increase the affinity for the substrate. There is no limitation on the organic solvent that can be used, and those generally contained in the ink can be used. For example, methanol, ethanol, propanol, butanol, hexanol, octanol, cyclohexanol, benzyl alcohol, phenol, ethylene glycol, diethylene glycol, Alcohols such as propylene glycol, dipropylene glycol, glycerin and terpineol, acetone, methyl ethyl ketone, methyl tertiary butyl ketone, ketones such as acetylacetone and acetophenone, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, diethylene glycol Monoalkyl ether, diethylene glycol dialkyl ether , Propylene glycol monoalkyl ether, propylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, ethers such as dipropylene glycol dialkyl ether, N, N-dimethylformamide, N-methylformamide, acetamide, N, N-dimethylacetamide, Examples include amides such as N-methylpyrrolidone, esters such as methyl formate, ethyl formate, ethyl acetate, dimethyl carbonate, ethylene carbonate, and propylene carbonate.
本発明のニッケルインク組成物は、加熱してニッケル金属膜を形成する。エチレンジアミン、エタノールアミン類を使用する場合、加熱温度は雰囲気によって異なるため、限定することは困難であるが、非酸化雰囲気、例えば、窒素、アルゴン、水素中で加熱する場合、１５０℃〜３００℃が好ましく、１７０℃〜２５０℃がさらに好ましい。高温で加熱するほど、生成したニッケル金属膜は緻密になり、膜中の不純物は少なくなるが、３００℃を超える温度で加熱しても、その効果は小さい。１５０℃未満で加熱した場合、ニッケル金属膜の生成には工業的でないほど長時間を要し、また不純物を多く含む膜が形成される。酸素濃度が５％以上の雰囲気で加熱する場合、加熱温度は１７０℃〜３００℃が好ましく、１８０℃〜２５０℃がさらに好ましい。酸素濃度が５％以上で加熱した場合、有機物が酸化され、ニッケル金属膜中に残存するため、非酸化雰囲気で加熱する場合より、高温が必要となる。 The nickel ink composition of the present invention is heated to form a nickel metal film. When ethylenediamine and ethanolamines are used, the heating temperature varies depending on the atmosphere, so it is difficult to limit, but when heating in a non-oxidizing atmosphere such as nitrogen, argon, or hydrogen, 150 ° C to 300 ° C is Preferably, 170 ° C to 250 ° C is more preferable. The higher the temperature is heated, the denser the nickel metal film that is produced and the fewer impurities in the film, but the effect is small even when heated at a temperature exceeding 300 ° C. When heated below 150 ° C., it takes a long time to produce a nickel metal film that is not industrial, and a film containing a large amount of impurities is formed. When heating in an atmosphere having an oxygen concentration of 5% or more, the heating temperature is preferably 170 ° C to 300 ° C, more preferably 180 ° C to 250 ° C. When heated at an oxygen concentration of 5% or higher, the organic matter is oxidized and remains in the nickel metal film, so that a higher temperature is required than when heating in a non-oxidizing atmosphere.
本発明のニッケルインク組成物は、高導電性を有することからコンデンサなどの電極を形成するニッケル膜に好適に使用され、微細配線化が可能であるなどの効果が期待できる。また、磁気シールドなどの用途にも使用することができる。 Since the nickel ink composition of the present invention has high conductivity, it can be suitably used for a nickel film for forming an electrode such as a capacitor, and effects such as enabling fine wiring can be expected. It can also be used for applications such as magnetic shielding.
本発明のニッケルインク組成物を基板に塗布した後、加熱することで、ニッケル金属膜を形成することができる。加熱温度が低いため、用いる基板に特に制限はなく、例えば、ＰＥＴ、ＰＥＮ、ＰＣ、ポリイミド、ナイロン、エポキシなどの樹脂、セラミックス、ガラス、紙等が使用できる。 A nickel metal film can be formed by applying the nickel ink composition of the present invention to a substrate and then heating. Since the heating temperature is low, the substrate to be used is not particularly limited. For example, a resin such as PET, PEN, PC, polyimide, nylon, and epoxy, ceramics, glass, paper, and the like can be used.
本発明を以下の実施例により更に詳細に説明するが、本発明はこれらに限定されるものではない。なお、表記を簡潔にするため、以下の略記号を使用した。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In order to simplify the notation, the following abbreviations were used.
ＮＦ：ギ酸ニッケル（ＩＩ）
ＮＦＨ：ギ酸ニッケル（ＩＩ）・２水塩
ＥＤＡ：エチレンジアミン
ＴＥＴＡ：トリエチレンテトラミン
ＭＥＡ：モノエタノールアミン
ＭＭＥＡ：Ｎ−メチルエタノールアミン
ＤＭＥＡ：Ｎ，Ｎ−ジメチルエタノールアミン
ＭＤＥＡ：Ｎ−メチルジエタノールアミン
ＥＧ：エチレングリコール
ＤＥＧ：ジエチレングリコール
ＢＤＧ：ジエチレングリコールモノブチルエーテル
ＡＡ：アセチルアセトン
ＤＭＦ：Ｎ，Ｎ−ジメチルホルムアミド
実施例１
ＮＦに対して２倍モルのＴＥＴＡを加え混合し、ニッケルインク組成物を調製した。これを１００μｍの厚さでガラス基板上に塗布した。窒素雰囲気下で２２０℃、３０分加熱し、ニッケル金属膜を得た。
NF: Nickel formate (II)
NFH: nickel (II) formate dihydrate EDA: ethylenediamine TETA: triethylenetetramine MEA: monoethanolamine MMEA: N-methylethanolamine DMEA: N, N-dimethylethanolamine MDEA: N-methyldiethanolamine EG: ethylene glycol DEG: Diethylene glycol BDG: Diethylene glycol monobutyl ether AA: Acetylacetone DMF: N, N-dimethylformamide Example 1
A nickel ink composition was prepared by adding 2 times mole of TETA to NF and mixing. This was apply | coated on the glass substrate with the thickness of 100 micrometers. The nickel metal film was obtained by heating at 220 ° C. for 30 minutes under a nitrogen atmosphere.
このニッケル金属膜の膜厚を光学顕微鏡で測定したところ、３．６６μｍだった。表面抵抗率を四探針法低抵抗率計で測定したところ、１．３４７Ω／□であり、体積抵抗は４９３μΩ・ｃｍであった。 The thickness of the nickel metal film was measured with an optical microscope and found to be 3.66 μm. When the surface resistivity was measured with a four-probe method low resistivity meter, it was 1.347 Ω / □, and the volume resistance was 493 μΩ · cm.
生成した膜のＸ線回折から、完全にニッケル金属になっており、酸化物は存在していなかかった。 From the X-ray diffraction of the formed film, it was completely nickel metal and no oxide was present.
比較例１
ＮＦに対して２倍モルのオクチルアミンを加え混合し、ニッケルインク組成物を調製した。これを１００μｍの厚さでガラス基板上に塗布した。窒素雰囲気下で２２０℃、３０分加熱した。
Comparative Example 1
A nickel ink composition was prepared by adding and mixing 2 moles of octylamine with respect to NF. This was apply | coated on the glass substrate with the thickness of 100 micrometers. Heated at 220 ° C. for 30 minutes in a nitrogen atmosphere.
この膜の表面抵抗率を四探針法低抵抗率計で測定したところ、導電性はなかった。 When the surface resistivity of this film was measured with a four-probe method low resistivity meter, there was no conductivity.
実施例２〜５
実施例１で調製したニッケルインク組成物を実施例１と同様の方法でガラス基板上に塗布し、窒素下、表１記載の温度で３０分加熱した。
生成した膜の体積抵抗を実施例１と同様に測定し、表１に記した。
Examples 2-5
The nickel ink composition prepared in Example 1 was applied on a glass substrate in the same manner as in Example 1, and heated at a temperature shown in Table 1 for 30 minutes under nitrogen.
The volume resistance of the produced film was measured in the same manner as in Example 1 and is shown in Table 1.
実施例６〜９
表２記載のモル比でＮＦとＴＥＴＡを混合し、ニッケルインク組成物を調製した。実施例１と同様の方法でガラス基板上に塗布し、窒素下、２３０℃で３０分加熱し、ニッケル膜を形成した。生成した膜の体積抵抗を実施例１と同様に測定し、表２に記した。
Examples 6-9
NF and TETA were mixed at a molar ratio shown in Table 2 to prepare a nickel ink composition. The same method as in Example 1 was applied on a glass substrate and heated at 230 ° C. for 30 minutes under nitrogen to form a nickel film. The volume resistance of the produced film was measured in the same manner as in Example 1 and listed in Table 2.
実施例１０
ＮＦＨ １ｇ、ＥＤＡ ２ｇ（ＥＤＡ／ＮＦＨのモル比 ６．２）、ＭＤＥＡ １ｇ（ＭＤＥＡ／ＮＦＨのモル比 １．６）、ＤＥＧ １ｇを混合し、ニッケルインク組成物を調製した。これを１００μｍの厚さでガラス基板上に塗布した。窒素雰囲気下で２３０℃、６０分加熱し、ニッケル金属膜を得た。
Example 10
NFH 1g, EDA 2g (EDA / NFH molar ratio 6.2), MDEA 1g (MDEA / NFH molar ratio 1.6), and DEG 1g were mixed to prepare a nickel ink composition. This was apply | coated on the glass substrate with the thickness of 100 micrometers. Heating was performed at 230 ° C. for 60 minutes in a nitrogen atmosphere to obtain a nickel metal film.
このニッケル金属膜の膜厚を段差計で測定したところ、２μｍであり、体積抵抗は５０ｍΩ・ｃｍであった。 When the thickness of the nickel metal film was measured with a step gauge, it was 2 μm and the volume resistance was 50 mΩ · cm.
比較例２
ＮＦＨ １ｇ、ＭＤＥＡ ２ｇ（ＭＤＥＡ／ＮＦＨのモル比 ３．２）、ＤＥＧ １ｇ、を混合したが、ＮＦがインク組成物に溶解せず、スラリー状態になった。このスラリー状インク組成物を１００μｍの厚さでガラス基板上に塗布した。窒素雰囲気下で２３０℃、６０分加熱したが、絶縁膜であり、ニッケル金属にならなかった。
Comparative Example 2
NFH 1 g, MDEA 2 g (MDEA / NFH molar ratio 3.2), and DEG 1 g were mixed, but NF did not dissolve in the ink composition and became a slurry state. The slurry ink composition was applied on a glass substrate with a thickness of 100 μm. Although it was heated at 230 ° C. for 60 minutes in a nitrogen atmosphere, it was an insulating film and did not become nickel metal.
実施例１１〜１８
ＮＦＨ １ｇを表３記載の組成と混合した。なお、表３記載の組成は、ＮＦＨに対するモル比で記した。こうして調製したニッケルインク組成物を実施例１と同様の方法でガラス基板上に塗布し、窒素下、表３記載の温度で６０分加熱した。
Examples 11-18
1 g of NFH was mixed with the composition described in Table 3. In addition, the composition of Table 3 was described by the molar ratio with respect to NFH. The nickel ink composition thus prepared was applied on a glass substrate in the same manner as in Example 1, and heated at a temperature shown in Table 3 for 60 minutes under nitrogen.
生成した膜の体積抵抗を実施例１と同様に測定し、表３に記した。 The volume resistance of the produced film was measured in the same manner as in Example 1 and listed in Table 3.
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