TW200903519A - Copper conductive paste, conductor circuit board, and electronic component - Google Patents
Copper conductive paste, conductor circuit board, and electronic component Download PDFInfo
- Publication number
- TW200903519A TW200903519A TW097102693A TW97102693A TW200903519A TW 200903519 A TW200903519 A TW 200903519A TW 097102693 A TW097102693 A TW 097102693A TW 97102693 A TW97102693 A TW 97102693A TW 200903519 A TW200903519 A TW 200903519A
- Authority
- TW
- Taiwan
- Prior art keywords
- copper
- glass frit
- glass
- paste
- copper conductor
- Prior art date
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 267
- 239000010949 copper Substances 0.000 title claims abstract description 204
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 201
- 239000004020 conductor Substances 0.000 title claims description 221
- 239000011521 glass Substances 0.000 claims abstract description 228
- 239000000843 powder Substances 0.000 claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 76
- 238000010304 firing Methods 0.000 claims description 54
- 229910000831 Steel Inorganic materials 0.000 claims description 23
- 239000010959 steel Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 22
- 238000009713 electroplating Methods 0.000 claims description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims 2
- 244000046052 Phaseolus vulgaris Species 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012298 atmosphere Substances 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000007747 plating Methods 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- -1 for example Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 206010036790 Productive cough Diseases 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- OUFLLVQXSGGKOV-UHFFFAOYSA-N copper ruthenium Chemical compound [Cu].[Ru].[Ru].[Ru] OUFLLVQXSGGKOV-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229960005489 paracetamol Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000001568 sexual effect Effects 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 210000003802 sputum Anatomy 0.000 description 2
- 208000024794 sputum Diseases 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 230000035922 thirst Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010068370 Glutens Proteins 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 206010061218 Inflammation Diseases 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- 229910052849 andalusite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- KAMGYJQEWVDJBD-UHFFFAOYSA-N bismuth zinc borate Chemical compound B([O-])([O-])[O-].[Zn+2].[Bi+3] KAMGYJQEWVDJBD-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005323 electroforming Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000021312 gluten Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012803 melt mixture Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000009725 powder blending Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
-
- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
Landscapes
- Power Engineering (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Glass Compositions (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Ceramic Capacitors (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
Description
200903519 九、發明說明： 【發明所屬之技術領域】 種用以形成電子零件之電路基板之導體 本發明係關於一 電路或積層電容器之外部電極等、以Cu為主體之銅導體 糊，又，係關於一種使用該銅導體糊而形成有導體膜或電 極之導體電路板，及電子零件。 【先前技術】200903519 IX. Description of the Invention: [Technical Field] The present invention relates to a copper conductor paste mainly composed of Cu, an external electrode of a circuit or a multilayer capacitor, and the like. A conductor circuit board in which a conductor film or an electrode is formed using the copper conductor paste, and an electronic component. [Prior Art]
為了於陶竟基板等絕緣基板之表面或内部，形成配線、 導電圖案、積層陶究電容器之電極等導電膜或電路，而廣 泛使用導電性糊。 導電性糊通常含有導電性金屬粉末及玻璃料作為固形成 分，為了對其賦予塗佈性，可藉由添加由適當樹脂或溶劑 所形成的媒劑進行混煉來製備。並且，藉由絲網印刷等將 導電性糊塗佈於絕緣基板之表面後，進行高溫加熱，藉此 =除有機成分，同時玻璃料溶融流動而促進金屬粉末之燒 、’'α，並最終燒結金屬粉臈，藉此可形成導體膜。 作為用於導電性糊之導電性粉末，主要有Au、Ag、A conductive paste is widely used for forming a conductive film or a circuit such as a wiring, a conductive pattern, or an electrode for stacking ceramic capacitors on the surface or inside of an insulating substrate such as a ceramic substrate. The conductive paste usually contains a conductive metal powder and a glass frit as a solid component, and can be prepared by kneading by adding a solvent formed of a suitable resin or a solvent in order to impart coatability thereto. Further, the conductive paste is applied to the surface of the insulating substrate by screen printing or the like, and then heated at a high temperature, whereby the organic component is removed, and the glass frit is melted and flowed to promote the burning of the metal powder, ''α, and finally sintered. Metal powder crucible whereby a conductor film can be formed. As the conductive powder for the conductive paste, there are mainly Au, Ag,
Pt、㈣貴金屬類型者，及Ni、Cu之賤金屬類型者。該等 之中，使用Cu作為導電性粉末之銅導體糊，具有如下優 :二因：料便宜，且具有優異之導電性及導熱性，故可獲 =—可罪〖生等，因而得到廣泛使用。此處，銅於環境中易 於虱化，若被氧化則導致焊接性大幅下降，故為了保護將 =導體糊進行塗佈.燒成所形成之銅導體膜不被氧化，而 θ 、接眭，多數情況是實施鋅、鎳、金等金屬電鍍處理 I2Sl59.doc 200903519 (例如，參照專利文獻1)。 然而，於將如上所述 糊進行塗佈·以㈣j U作料電性粉末之銅導體 “ 凡成而形成銅導體臈時，存在兩大問題。 "二之一問題點在於：於基板等素體上，將銅導體糊進 行k佈·燒成而形成銅導體 ^ ^ Λ ^ 腰時’銅導體膜與基板等之审 接力焚到燒成氣體環境之較 二植Λ 4 大影響。即’為了防止銅氧化 而導致導電性下降，必須使 乳 體環境中，例如峨氫衰 成非氧化性氣 ,t ^ 戈乳-亂氣等惰性氣體環境中或還 原性軋體環境中進行。且， 一 氣體環境中進行燒成，導電^ 於此種非氧化性 黏接性等亦優異之銅導體 必須使用即便於非氧化性氣體環境中進行燒成，亦 : 的耐還原性，並具有低軟化點，對銅粉或基板且 有良好潤濕性之玻璃，來作為銅導體糊t所含之玻璃料Γ 並且，先前是使用含鉛之低炫點玻璃來作為此種玻璃料 (例如’參照專利文獻1)。 但，因錯有毒，故近年來多次提出無錯低熔點玻璃。於 燒成氣體環境中完全不含氧氣時，多數情況是該等無錯低 k點玻璃之黏接效果低，導致所燒成之銅導體膜之黏接力 下降口此it㊉於燒成氣體環境中添加微量之氧氣（數 ppm〜1〇〇PPm左右）（參照非專利文獻1)。又，亦提出有如 下方法：代替燒成時之導入微量氧氣’而於燒成步驟之前 設置於2〇(TC左右之空氣中的氧化步驟而預先氧化一部分 銅之方法（參照專利文獻2)，於銅導體物中調配氧化銅粉末 之方法（參照專利文獻〗），將燒成時釋放氧氣之物質添加於 128159.doc 200903519 銅導體糊之方法（參照專利文獻^等。 然而，由於氧氣之需要量為 ^ 體糊之塗膜之形狀或厚度等而有：不：我：需要量因銅導 令，均難以把握及控制氧氣之適 ^此上述各方法 足’則密接力下降，若過詈，目f 、'且，若氧氣量不 性及焊接性下降，由於 ^於崎“造成電氣特 黏接力、電氣特性、焊::::頻::結:銅導體膜之 .，、、鉛低熔點玻璃作為玻璃 σ ' 發揮重要仙，料m對表現密接力 穩定並存。 實難以使表現密接力與抑制銅氧化 為了解決該問題，提出有使 觸_以下，且由含有“境中對銅板之接 3有Ζη及Cu之硼矽玻璃所形成之玻 璃料(參照專利文獻4)。藉由使用具有此種潤濕性之玻璃 料而易於控制燒成氣體環境。但，玻璃料與銅板之接觸 角較大地不同於玻璃料對實際用於銅導體糊之銅粉的潤渴 性二即便玻璃料與銅板之接觸角為9〇度以下，亦難以穩定 獲得具有良好密接性之銅導體膜。 另問題點在於：對燒成之銅導體膜實施電解或無電解 電鍵而進仃金屬電鍍處理時，銅導體膜中之玻璃成分由於 s夂性電m發生變f並溶解，玻璃結構遭到破壞，而導 致銅導體膜與基板之黏接強度大幅下降…亦有如下問 題.由於電鍍液自玻璃成分之溶解部分或銅導體膜中之空 隙等滲入銅導體膜中，而導致絕緣電阻下降或產生裂縫， 此外引起所謂"焊錫爆裂現象”，即，所滲入之電鍍液於回 128159.doc 200903519 焊時被加熱而氣化’熔融之焊錫發生飛濺。 因此，用於銅導體糊之玻璃要求酸性電鍍液難以滲入， 且可形成緻密之銅導體膜的特性。先前，根據此種目的， 研究使用si成分較多的鹼矽酸鹽玻璃（參照專利文獻5、 6)。但，此種玻璃因對銅粉之潤濕性差，又，軟化點高等 理由’而難以獲得具有良好密接力之銅導體膜。 又，如上述專利文獻4所揭示之含有大量氧化鋅（Zn〇)之 玻璃系玻璃料，由於對銅之潤濕性良好，因此可獲得初始 密接力高之銅導體膜，並可解決上述第一問題點，但由於 該種玻璃之耐酸性差，因此存在電鍍時密接力大幅下降之 問題，因而無法解決第二問題。 [專利文獻1]日本專利特開平6_342965號公報 [非專利文獻1 ]電子材料，工業調查會股份有限公司， 昭和63年5月1日’ 1988年5月號，第53〜56頁 [專利文獻2]曰本專利特開平8-17241號公報 [專利文獻3 ]日本專利特開平5 -1 〇 1 7 0 7號公報 [專利文獻4]曰本專利特開平1丨-260146號公報 [專利文獻5]日本專利特開20〇3_347148號公報 [專利文獻6]日本專利特開2〇〇2_25337號公報 【發明内容】 [發明所欲解決之問題] 如上所述’將銅導體糊進行塗佈.燒成而形成銅導體膜 蚧，鋼導體膜之密接力受到燒成氣體環境之較大影響，尤 其是使用無鉛玻璃之玻璃料時，燒成時必須向惰性氣體環 128159.doc 200903519 境中添加微量之氧惫黧 量，由於M… 難以把握及控制其適當的添加 良等之第 之不均，而存在產生黏接力下降或焊接不 糊所声Γ 又’使用含有無錯玻璃作為玻璃料之銅 2 ΐ成之銅導體膜，存在即便初始密接力高，電鍍處理 後之搶接力'亦大幅下降之第n 又 、因此’業者謀求—種銅導體糊，其係即便未Pt, (4) Types of precious metals, and those of Ni and Cu. Among these, copper conductor paste using Cu as a conductive powder has the following advantages: Secondly, it is inexpensive, and has excellent electrical conductivity and thermal conductivity, so that it can be obtained as a sin. use. Here, copper is easily deuterated in the environment, and if it is oxidized, the solderability is greatly lowered. Therefore, in order to protect the conductor paste, the copper conductor film formed by firing is not oxidized, and θ and the junction are In many cases, metal plating treatment such as zinc, nickel, gold, or the like is performed. I2Sl59.doc 200903519 (for example, refer to Patent Document 1). However, there are two major problems when coating the paste as described above and forming a copper conductor with a copper conductor of (4) j U as an electrical powder. One of the two problems is that the substrate and the like are In the body, the copper conductor paste is k-baked and fired to form a copper conductor. ^ ^ Λ ^ When the waist, the copper conductor film and the substrate are in contact with each other and burned into the firing gas environment. In order to prevent the oxidation of copper and cause a decrease in conductivity, it is necessary to carry out the environment in the emulsion, for example, hydrogen fading into a non-oxidizing gas, in an inert gas atmosphere such as t-go milk or disordered gas, or in a reducing rolling environment. When it is fired in a gas atmosphere, the copper conductor which is excellent in such non-oxidative adhesion and the like must be fired even in a non-oxidizing gas atmosphere, and has low reduction resistance and low softening. Point, a glass with good wettability to copper powder or substrate, as a glass frit contained in the copper conductor paste t. Previously, a low-point glass containing lead was used as the glass frit (for example, 'refer to Patent Document 1). However, due to toxic, Therefore, in recent years, the error-free low-melting glass has been proposed many times. When the oxygen is completely contained in the firing gas environment, in most cases, the bonding effect of the error-free low-k glass is low, resulting in the sintered copper conductor film. In the case where the adhesive force is lowered, a small amount of oxygen (a few ppm to 1 〇〇 PPm) is added to the firing gas atmosphere (see Non-Patent Document 1). Further, there is also proposed a method of introducing a trace amount of oxygen instead of firing. 'A method of preparing a copper oxide powder in a copper conductor by a method of oxidizing a part of copper in an air oxidation step of about 2 Torr (refer to Patent Document 2) before the calcination step (refer to the patent literature) The method of adding a substance for releasing oxygen at the time of firing to 128159.doc 200903519 copper conductor paste (refer to the patent document ^ etc. However, since the required amount of oxygen is the shape or thickness of the coating film of the body paste, etc.: No: I: The amount of copper required is difficult to grasp and control the oxygen. The above methods are sufficient to reduce the adhesion. If the temperature is too low, the amount of oxygen is not good and the weldability is degraded. , Because ^Usaki "causes electrical special adhesion, electrical characteristics, welding::::frequency::junction: copper conductor film.,, lead low-melting glass as glass σ' play an important immortal, material m on the performance of the adhesion Stable and coexisting. It is difficult to make the performance of the adhesion and inhibit the oxidation of copper. In order to solve this problem, it is proposed to have a glass frit formed by the borax glass containing the Ζ 及 and Cu in the interface of the copper plate ( Refer to Patent Document 4). It is easy to control the firing gas environment by using a glass frit having such wettability. However, the contact angle between the glass frit and the copper plate is largely different from that of the glass frit actually used for the copper conductor paste. The thirst of the powder is two. Even if the contact angle between the glass frit and the copper plate is 9 degrees or less, it is difficult to stably obtain a copper conductor film having good adhesion. Another problem is that when the sintered copper conductor film is subjected to electrolysis or electroless electrolysis, and the metal plating treatment is performed, the glass component in the copper conductor film is f-dissolved due to the s-electricity m, and the glass structure is destroyed. The adhesion strength between the copper conductor film and the substrate is greatly reduced. The following problems occur. Since the plating solution penetrates into the copper conductor film from the dissolved portion of the glass component or the void in the copper conductor film, the insulation resistance is lowered or generated. The crack, in addition, causes the so-called "solder burst phenomenon", that is, the plating solution that is infiltrated is heated back to 128159.doc 200903519 and is vaporized. The molten solder is splashed. Therefore, the glass used for the copper conductor paste requires acidity. The plating solution is difficult to infiltrate, and the characteristics of the dense copper conductor film can be formed. Previously, alkali silicate glass having a large amount of si component has been studied for the purpose (see Patent Documents 5 and 6). It is difficult to obtain a copper conductor film having good adhesion to the copper powder because of poor wettability and high softening point. Further, as disclosed in the above Patent Document 4 A large amount of zinc oxide (Zn〇) glass-based glass frit has good wettability to copper, so that a copper conductor film having a high initial adhesion can be obtained, and the above first problem can be solved, but the acid resistance of the glass is However, there is a problem that the adhesion is greatly reduced at the time of electroplating, and the second problem cannot be solved. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 6-342965 [Non-Patent Document 1] Electronic Materials, Industrial Investigations Co., Ltd., Showa 63 May 1st, 1988, May 1988, pp. 53-56 [Patent Document 2] Japanese Patent Laid-Open No. Hei 8-17241 [Patent Document 3] Japanese Patent Laid-Open No. 5 -1 〇1 7 0 7 [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problems to be Solved by the Invention] As described above, the copper conductor paste is coated and fired to form a copper conductor film. The adhesion of the steel conductor film is greatly affected by the atmosphere of the firing gas, especially the use of lead-free glass. Glass frit When firing, it is necessary to add a small amount of oxygen to the inert gas ring 128159.doc 200903519. Since M... is difficult to grasp and control the unevenness of the proper addition, there is a drop in adhesion or welding. I don’t know what to say, and I’ve used the copper conductor film containing copper without error glass as the glass frit. Even if the initial adhesion is high, the grabbing force after plating is greatly reduced. Seeking for a kind of copper conductor paste, even if it is not
成時之氣體環境，亦可獲得高密接力，並可形成電好: 後之密接力下降亦少之銅導體膜者。 、又处J :::明係鑒於上述方面而成者，其目的在於提供 =格控制燒成時之氣體環境，亦可獲得高密接力，並 了形成耐電鑛性良好1雷供者 &好且電鍍處理|之密接力了降亦少之銦 導體膜的銅導體糊，又，其目的於一 ^ σ 導體電路板及電子零件。、 、7、一可靠性高之 [解決問題之技術手段] ^發明者等人it行努力研究之結果發現：將㈣體糊進 4成所形成之銅導體膜之密接力，根據燒成氣體環境而 敏感地變化，其原因在於玻璃料對銅粉之潤濕性與鋼粉表 ，之氧化程度大有關聯；從而完成本發明（參照表工之與 氧化銅粉膜及氧化銅粉膜之接觸角）。 一 、即，普通玻璃料對存在氧化膜之銅粉表面具有良好之潤 濕性，但對未氧化之銅粉表面之㈣性差0若麵料對2 氧化之銅粉之潤濕性差，則無法於燒成銅導體糊時破璃料 對銅粉進行充分且均勾的潤濕，無法於基板與所燒成之 導體膜之間形成緻密且均勻的玻璃結合層，因此銅導體膜 128159.doc 200903519 =力下降…若玻璃料對鋼粉之潤濕性差，則對於 燒成知之破璃料之炼融流動，銅粉無法與其保持-致’因 而銅粉之燒結性下降，成為办 .、、、工隙車乂夕之鋼導體膜。此種銅 導體膜之熱或電氣特性差， 電鑛液易於滲入至銅導體膜之内^步驟中，酸性或驗性 人 主例導體膜之内部或銅導體膜與基板之結 :面，而侵敍接合界面之金屬或玻璃、陶竟等基板之質 地，從而使銅導體膜與基板之密接力下降。 二基於此種見解，本發明者等人發現：若使用對未 =之銅粉亦具有良好潤濕性之玻璃料，則即便燒成時未 。控制氣體環境’亦可獲得具有良好密接力之銅導體 ^但，對未氧化之銅粉具有良好潤濕性之該種玻璃料， 雖大有助於提高燒結性及初始密接力，但由於耐酸 不充分，因此仍留有銅導體膜之耐電鑛性問題。因此，本 發明者等人發現：若於該種玻璃料中併用滿足特定條件之 性等耐化學藥品性之玻璃料，則表現兩種玻璃料 目叫乍用，可獲得密接性、对電錢性均非常良好之銅導 體膜；從而完成本發明。 因此，本發明之請求項1之銅導體糊之特徵在於，笪至 2有以銅粉為主體之導電性粉末、玻璃料、有機媒劑而 ^ ’且作為玻璃料’至少含有有助於提高潤濕性之第一 玻璃料、及有助於提高财化學藥品性之第二破璃料，並且 弟一玻璃料與第二玻璃料滿足下述條件。 严（1)第一玻璃料之軟化點為8〇〇r以下，且於90(rc之氮 孔衣去見中’對由實質上表面未被氧化之銅粉所形成之媒的 128159.doc 200903519 接觸角為60度以下。 ⑺第二玻璃料於25t#1Qf量％漠度硫酸水溶液之溶解 度為1 mg/cm2.hr以下。 (3)第一玻璃料之軟化點與第二破璃料之軟化點 15〇t以下。 <左馬 。⑷相對於玻璃料總量，第―麵料之含量為ig〜7〇質量 °/〇,第二玻璃料之含量為30〜90質量％。 性明，可藉由併用作為破璃料之有助於提高潤濕 第麵料、及有助於提高耐化學藥品性之第二 =表：兩者之相乘效果，即便未嚴格控制燒成時之氣 亦可獲得高密接力，並且可形成耐電錢性良好且 電鍍處理後之密接力下降亦少之銅導體膜。 又’請求項2之發明如請求項1之銅導體糊，其中上述第 一玻璃料之軟化點為70CTC以下。 :據該發明，第一玻璃料之燒成時之流動性高，可實現 的潤濕’較大地有助於提高燒結性及密接性。 :二請求項3之發明如請求項⑷之銅導體糊，其中上 ㈣破螭料與上述條件下之銅粉之接觸角為45度以下。 牛提❹H璃料之燒成時之潤濕性高，可進-銅導體臈之密接力。 又’睛求項4之發明如士太出= 糊，发中上、十.Λ & 明求項1至3中任一項之銅導體 2 4玻璃料係實質上不含鉛之無鉛玻璃。 :據：發明，可提供無害且不污染環境之銅導體糊。 @求項5之發明如請求項1至4中任-項之銅導體 I28l59.doc 200903519 糊’其_玻璃料係實晳 伸^質上不含鉍之無鉍玻璃。 根據S亥發明，可摇 鏞右次潘、使用有害性資訊不充分’又’為 稀有貝源之级，亦可谨γ ή 獲侍良好性能之銅導體糊。 又，請求項ό之發明如这 ^ Φ^ . 明求項1至5中任一項之銅導體In the gaseous environment of the time, the high-density relay can also be obtained, and the electric conductor can be formed: the copper conductor film with less dense contact force after the reduction. In addition to J:: Ming Department, in view of the above aspects, the purpose is to provide a gas environment for controlling the firing, and also to obtain a high-density relay, and to form a good resistance to electric ore 1 mine donor & good And the electroplating treatment|the copper conductor paste of the indium conductor film which has a small contact force is also less, and the purpose is the one σ conductor circuit board and an electronic component. , 7, and a high reliability [technical means to solve the problem] ^Inventors and others have tried hard to find the result: the adhesion of the copper conductor film formed by the (4) body paste into 40%, according to the firing gas Environmentally and sensitively, the reason is that the wettability of the glass frit to the copper powder is greatly related to the degree of oxidation of the steel powder table; thus completing the present invention (refer to the surface of the copper oxide powder film and the copper oxide powder film) Contact angle). First, the ordinary glass frit has good wettability on the surface of the copper powder with oxide film, but the difference in the surface of the unoxidized copper powder is 0. If the wettability of the copper powder of the 2 oxidized fabric is poor, it cannot be When the copper conductor paste is fired, the glass frit is sufficiently wetted and wetted, and a dense and uniform glass bonding layer cannot be formed between the substrate and the fired conductor film. Therefore, the copper conductor film 128159.doc 200903519 = force drop... If the wettability of the glass frit to the steel powder is poor, the copper powder cannot be kept in the smelting flow of the glass frit, and thus the sinterability of the copper powder is reduced, and the sinterability of the copper powder is reduced. The steel conductor film of the stern car. The copper conductor film is inferior in thermal or electrical properties, and the electromineral liquid is easily infiltrated into the copper conductor film in the step of acid or inspecting the inside of the main conductor film or the junction of the copper conductor film and the substrate: The texture of the substrate such as metal or glass or ceramics is invaded at the joint interface, so that the adhesion between the copper conductor film and the substrate is lowered. Based on this finding, the inventors of the present invention have found that a glass frit having good wettability to copper powder which is not = is not used even at the time of firing. The controlled gas environment 'can also obtain a copper conductor with good adhesion. However, the glass frit having good wettability to unoxidized copper powder greatly contributes to the improvement of sinterability and initial adhesion, but is resistant to acid. Insufficient, so there is still a problem of resistance to electrical conductivity of the copper conductor film. Therefore, the present inventors have found that if a glass frit resistant to chemical properties such as a specific condition is used in combination with the glass frit, two types of glass materials are used for the purpose of obtaining adhesion and electricity. A copper conductor film having a very good property; thus completing the present invention. Therefore, the copper conductor paste of claim 1 of the present invention is characterized in that 笪 to 2 has a conductive powder mainly composed of copper powder, a glass frit, and an organic vehicle, and at least contains as a glass frit to contribute to improvement. The first glass frit of wettability and the second glass frit which contributes to the improvement of chemical properties, and the first glass frit and the second glass frit satisfy the following conditions. Strict (1) The softening point of the first frit is 8 〇〇r or less, and at 90 (the nitrogen hole of rc is seen in the '128159.doc of the medium formed by the copper powder which is not oxidized substantially on the surface) 200903519 The contact angle is below 60 degrees. (7) The solubility of the second glass frit in the 25t#1Qf%% sulfuric acid aqueous solution is below 1 mg/cm2.hr. (3) The softening point of the first frit and the second glass frit The softening point is 15 〇t or less. <Left horse. (4) The content of the first fabric is ig~7〇 mass °/〇, and the content of the second glass frit is 30 to 90% by mass relative to the total amount of the glass frit. It can be used as a glass frit to improve the wetting of the fabric and to improve the chemical resistance of the second = table: the synergy effect of the two, even if the firing is not strictly controlled The gas can also obtain a high-density relay, and can form a copper conductor film which is excellent in resistance to electric money and has a small decrease in the adhesion after the plating treatment. The invention of claim 2, wherein the first glass is the copper conductor paste of claim 1 The softening point of the material is below 70 CTC. According to the invention, the fluidity of the first glass frit is high during firing. The current wetting 'is greatly improved to improve the sinterability and the adhesion. The invention of claim 3 is the copper conductor paste of claim 4, wherein the contact angle of the upper (four) breaking material with the copper powder under the above conditions is 45 degrees or less. The high wettability of the sirloin H glass material can be entered into the copper conductor 臈. The invention of the eye 4 is such as Shitai = paste, hair in the upper, ten.铜 & The copper conductor 2 4 glass frit according to any one of items 1 to 3 is a lead-free glass substantially free of lead. According to the invention, a copper conductor paste which is harmless and does not pollute the environment can be provided. The invention of 5 is as claimed in claims 1 to 4 of the copper conductor I28l59.doc 200903519 paste 'its _ glass frit is finely stretched without enamel-free glass. According to S Hai invention, can shake right Sub-Pan, the use of harmful information is not sufficient 'again' is a rare source of the source, but also γ ή to get a good performance of the copper conductor paste. Also, the invention of the request item is like this ^ Φ^. Copper conductor to any of 5
糊其中進而含有氧化#H 根據該發明，破璃料 潤濕性之第-破璃料之/ 升’可減少有助於提高 藥品性之第二被②、,.配置，而增加有助於提高耐化學 理後之密接Λ #之調配量，可形成進-步降低電鍍處 理後之被接力下降的銅導體膜。 、、之發明如請求項1至6中任一項之銅導體 ^其中玻璃料對鋼粉（包括氧化銅粉）之調配比率係，相 於_質讀之銅粉，玻璃料為2〜2Qf量份之範圍。 根據該發明，所植々 疋成之鋼導體膜之耐電鍍性良好，可形 成進-步降低電鑛處理後之密接力下降之銅導體膜。 本發明之請求項8之導體雷 由將如請求項中路板，其特徵在於，其係藉 、 中任一項之銅導體糊塗佈於耐熱性基板 …加以坧成而形成銅導體膜所得者。 發明’可獲得形成有密接力良好且耐電鐘性優異 之銅導體膜的導體電路板。 又，請求項9之發明如請求項8之導體電路板，其中财熱 性基板係陶瓷基板。 根據該發明，可提供高可靠性之導體電路板。 究：板請求項W之發明係使用氧化銘或氮化銘基板作為陶 I28I59.doc 200903519 根據:發明，可提供便宜且高可靠性之導體電路板。 月東項11之發明如請求項8至丨时任—項之導體電 中其係於銅導體膜之表面，實施電解電鑛或無電 解電鍍形成金屬鍍層而成者。 二艮_明’可利用金屬鑛層防止銅導體膜氧化，從而 可β供回可罪性且焊接性優異之導體電路基板。 =明之請求項12之電子零件，其特徵在於，其係含有 如1月求項8至11中任-項之導體電路板而成者。 根據該發明，可提供可靠性良好之電子零件。 又，請求項u之發明係含有將如請求項⑴中任一項之 銅導體糊進行塗佈、燒成所形成之外部電極者。、 根據該發明，可提供可靠性良好之電子零件。 [發明之效果] 根據本發明之銅導體糊，可藉由併用作為玻璃 助於提高潤濕性之第-玻璃料、及有助於提高耐化學率 “生之第二玻璃料’而表現兩者之相乘效果，即 格控制燒成時之氣體環境，亦可獲得高密接力，並可妒 成耐電鍍性良好且錢處理後之密接力下降 道 體膜。 、則导 又 ，使用該銅導體糊，可獲得可靠性良好 及電子零件。【實施方式】 以下，說明用以實施本發明之最佳形態。 本發明之銅導體糊含有導電性粉末、玻璃料 之導體電路板 及有機媒劑 128159.doc -13· 200903519 而形成。 作為導電性粉末，使用主要含有銅粉者。較好的β 占導電性粉末中之6。質量%以上，導電二=銅粉 為銅粉。作為机 電眭柘末之全部亦可 作為銅私以外之導電性粉末， 使用 A"g，、Pd、Ni、Co#。，，期限… 於使用銅粉作為導電性粉末時，銅 特別限定，根據銅粒子之燒結性、目標鋼導體無 千滑性、緻密性等進行適當又 導麯膊品一 彳一就形成緻密之銅 較好的是併用粒徑不同之兩種以上粒 ::中於平均粒徑超過…(上限為〜左右)之銅 均叔徑為1 μΐΏ以下之微細銅粉者。進而，亦可 合:=1使之達到最密填充。如此於大粒徑銅粉中混 門廿、田5杈’由此可使微細銅粉混入大粒徑銅粉之 間’並緻密地填充鋼粉，從而提高銅導體 =之 微細銅粉之下* — 守蒞膜之電軋特性。 右。又、 無特別設定’實用上，下限為1 _左 又，从細銅粉之混合率係相對於100 銅粉，敕妊沾βΘ里仿之大粒徑 為銅於之大4:〜30質量份之範圍。不以上述方式併用作 ’ ^ ’立杈與微細粒徑銅粉時，銅粉較好的是使用芈 均粒捏未達W若使用平均：好的疋使用+ 於2ΓΓ鋼導體膜之緻密性或平滑性下降之虞。 璃料、：有助/璃科係併用有助於提高濁濕性之第-破 二等第:一學藥品性之第二玻璃料者。並 ⑴第 璃枓與弟二玻璃料’必須滿足以下條件。 第一玻璃料之軟化點為崎以下，且於峨之氮 128l59.doc •14- 200903519 氣環境中，與由實皙'士斤，， 耳為上表面未被氧化之銅粉所形成之膜的 接觸角為60度以下。 ()第玻璃料於饥對1G質量％濃度硫酸水溶液之溶 解度為1 以下。 (3) 第玻璃料之軟化點與第二玻璃料之軟化點之差為 1 5 0°C以下。 (4) 相對於破螭料總量，一 乐玻·瑪枓之含量為10〜70質量 %，第二玻璃料之含量為3〇〜9〇質量％。 玻璃通常係選自Pb、ς; r> .. 、B、鹼金屬、鹼土類金屬、The paste further contains oxidized #H. According to the invention, the wettability of the glass frit/ liters can reduce the second quilt, which contributes to the improvement of the medicinal properties, and the increase is helpful. By increasing the amount of the chemically bonded Λ#, it is possible to form a copper conductor film which is reduced in the contact force after the plating treatment. The invention is the copper conductor of any one of claims 1 to 6, wherein the ratio of the glass frit to the steel powder (including the copper oxide powder) is the copper powder of the _ quality reading, and the glass frit is 2 to 2 Qf. The range of parts. According to the invention, the steel conductor film of the vegetable tantalum is excellent in electroplating resistance, and a copper conductor film having a reduced adhesion after the electric ore treatment can be formed. The conductor of claim 8 of the present invention is characterized in that the copper conductor paste according to any one of the claims is applied to a heat-resistant substrate to form a copper conductor film. Invention A conductor circuit board in which a copper conductor film having excellent adhesion and excellent electric resistance is formed can be obtained. Further, the invention of claim 9 is the conductor circuit board of claim 8, wherein the heat-generating substrate is a ceramic substrate. According to the invention, a highly reliable conductor circuit board can be provided. Research: The invention of the board request item W uses Oxidation or Nitride substrate as a ceramic I28I59.doc 200903519 According to the invention, an inexpensive and highly reliable conductor circuit board can be provided. The invention of the moon east 11 is the conductor of the item 8 to 丨, which is attached to the surface of the copper conductor film, and is formed by electrolyzing or electroless plating to form a metal plating layer. In the second layer, the metal ore layer can be used to prevent the copper conductor film from being oxidized, so that the conductor circuit substrate which is sinful and excellent in solderability can be supplied. The electronic component of claim 12, which is characterized in that it comprises a conductor circuit board such as any one of items 8 to 11 of January. According to the invention, it is possible to provide an electronic component with good reliability. Further, the invention of claim u includes an external electrode formed by coating and firing a copper conductor paste according to any one of claims (1). According to the invention, it is possible to provide an electronic component with good reliability. [Effects of the Invention] The copper conductor paste according to the present invention can be used in combination with a first glass frit which contributes to the improvement of wettability as a glass, and a "second glass frit which contributes to the improvement of the chemical resistance rate". The multiplication effect of the person, that is, the gas environment during the control of firing, can also obtain a high-density relay, and can be made into a good electroplating resistance and the adhesion after the money treatment is reduced. The guide film is used again. In the conductor paste, the reliability and the electronic component are obtained. [Embodiment] Hereinafter, the best mode for carrying out the invention will be described. The copper conductor paste of the present invention contains a conductive powder, a glass frit conductor circuit board, and an organic vehicle. 128159.doc -13· 200903519 is formed. As the conductive powder, those mainly containing copper powder are used. Preferably, β accounts for 6 mass% or more of the conductive powder, and conductive copper = copper powder is copper powder. All of the powders can be used as conductive powders other than copper, using A"g, Pd, Ni, Co#.,, .... When copper powder is used as the conductive powder, copper is particularly limited, according to copper particles. Burn Sexual and target steel conductors without thousands of slipperiness, compactness, etc., and appropriate to guide the body of the product to form a dense copper. It is better to use two or more kinds of particles with different particle sizes: in the average particle size exceeds... (The upper limit is ~~) The fine copper powder with a copper unequal diameter of 1 μΐΏ or less. Further, it can be combined with: = 1 to achieve the closest filling. Thus, in the large-diameter copper powder, the threshold is mixed.杈 'This allows the fine copper powder to be mixed between the large-sized copper powder' and densely fills the steel powder, thereby increasing the copper conductor = under the fine copper powder * - the electric rolling characteristics of the Shou film. Right. There is no special setting 'practical, the lower limit is 1 _ left and the mixing ratio from fine copper powder is relative to 100 copper powder, and the large particle size of the 沾 沾 沾 Θ Θ Θ 仿 仿 仿 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Scope. When not used in the above manner and used as '^' vertical and fine-grained copper powder, it is better to use 芈 粒 粒 若 若 if the average is used: good 疋 use + in 2 ΓΓ steel conductor film The result of the decrease in compactness or smoothness. Glass material: The help of the glass/system is used to improve the turbidity of the first-breaking second-class: The first condition of the drug-based second glass frit. (1) The first glass material and the second glass frit 'must meet the following conditions. The softening point of the first glass frit is below the stagnation, and the nitrogen in the sputum is 128l59.doc •14- 200903519 In the gas environment, the contact angle with the film formed by the copper powder which is not oxidized on the upper surface is 60 degrees or less. () The glass frit is in the hunger to 1G mass% aqueous solution of sulfuric acid The solubility is less than 1. (3) The difference between the softening point of the first glass frit and the softening point of the second glass frit is below 150 ° C. (4) Relative to the total amount of broken materials, a Lebo·Ma Yuzhi The content is 10 to 70% by mass, and the content of the second glass frit is 3 〇 to 9 〇 by mass. The glass is usually selected from the group consisting of Pb and bismuth; r>., B, alkali metal, alkaline earth metal,
Zn、Al、Ti、Zr、Bi等的金眉之氧扎队 屬之乳化物之混合物，其軟化 占、潤濕性、耐酸性等耐 ^ D θ 兀予樂0口性荨啫多物性因氧化物 種類及2：而發生變化。本 發月之第一玻璃料及第二玻璃料 之種頰及組成並無特別限 即可。 刀別滿足上述（I)〜（4)之要件 並且，本發明令作為破 較好的暑佶用π入 就私纟兄問題之觀點而言，Zn, Al, Ti, Zr, Bi, etc., a mixture of emulsions of the genus Oxygen, which has softening, wettability, acid resistance, etc., and resistance to D θ 兀The type of oxide and 2: change. The cheeks and composition of the first frit and the second frit of this month are not particularly limited. The knives satisfy the requirements of (I) to (4) above, and the present invention makes the use of π into the problem of private brothers as a better summer.
Kj 3釔之無鉛玻璃。作為不含鉛且 條件之第一玻璃料，， " 八夕αη A J ~自U Sl〇2-B203 Jn〇為主成 刀之硼矽酸鋅系玻璃、以s R，〇(R為鹼金屬，R，為 2 2 3 _ 2〇4Si〇2-B2〇3_ 璃。^為主成分之蝴石夕酸系玻 瑪由於Zno具有提高與銅之潤濕 是含於第一破璁粗+ 果因此較好的 第二破璃料1 了上述㈣〇 /且滿足上述要件之 ^ ^^-B2〇3-R2LtSi〇n〇4i^^^^^ 屬，R,為驗土類金屬）為主2之1 2-B2〇3_R,0(R為驗金 成刀之卿酸系破璃以外，可選 I28159.doc 200903519 自以BhOrSiO2為主成分之鉍系玻璃等。再者，由於鉍為 稀有資源，且有害性資訊仍不充分，因此較好的是避免使 用。 此處第玻璃料係將銅導體糊塗佈於基板而進行燒成 夺潤濕銅粕促進燒結，並起到所燒成之銅導體膜與基板 間之接合劑的作用者。即，若燒成溫度為第一玻璃料之軟 …、上則第玻璃料潤濕銅粉並炫融流動，鋼粉亦與 丨-致進行移動以達到緻密。並且，若燒成溫度達到銅粉 之燒結溫度，則銅#間開始燒肖，於此種條件下燒成所得 之銅導體膜較緻密，並且玻璃接合層均句擴散至銅導體膜 與基板之間，可獲得銅導體膜之高接合強度。若第一玻璃 料之潤濕性低，則熔融玻璃無法於銅粉間平滑移動，無法 起到燒結助劑的作用，並且亦無法充分發揮作為銅導體膜 〃基板間之接合層的作用。結果燒成所得之銅導體膜之燒 結不良，銅導體膜與基板間之密接力下降，又，銅導體^ 因燒結不良且緻密性變差，因此電鑛時之電錢液易於“ 至接合層，接合層被電鑛⑨渗入之電鑛後的密接力大 低。 因此，為了確保塗佈銅導體糊所得之銅導體膜之密接 力’如上述要件⑴所示，必須具有第—玻璃料與銅粉之接 觸角為60度以下之潤濕性。為了獲得更好之密接力，更好 的是破璃料與銅粉之接觸角為45度以下。玻璃料與銅粉之 接觸角越低越好，因此並不特別設定下限。 此處，作為評價銅導體糊中玻璃料對銅粉之潤濕性的方 128l59.doc 16- 200903519 法’先前以來提出有評價破璃料對銅 (參照上述專利文獻4)β作 ，.、、角之方法 根據本發明者等人之研#处莫 =實際的銅導體糊中之鋼粉之形狀及表面狀態均= 2於銅板，對銅板之評價結果並未準確反映對實際的 銅導體糊中之銅粉之潤濕性、、 璃料對銅導體糊中之銅粉之潤渴^開發一種準確評價玻 性評價對象，直接使用實p ^方去。即，作為潤濕 祓便用實際的銅導體糊中所使用之 於類似於銅導體糊燒成時 ' 刀 下表示其方法。 f之狀&下補玻璃之潤濕性。以 首先，製備自與銅導體& 门 相同之組成僅去除玻璃料而得 玻璃銅導體糊，使用25〇網眼之不鏽鋼絲網，將兮益 玻璃銅導體糊整面絲網印刷於3英忖χ3英吁之氧化紹基板 上。繼而，利用12 〇 之、矣π 。 播 y k風乾燥機加熱2〇分鐘而使溶劑 揮發，之後，於氮氧 兄下，於300t下保持10分鐘，分 去除一部分有機媒劑，獲得附著於氧化銘基板上 約為30 銅粉膜。繼 又 置覆製加工成直徑為5軸、古戶如此所仔之鋼粉膜上，載 扒古^丨m嫌 门又為5 mm大小之玻璃料之 私末，利用以爐，於氧氣濃度為 下，於9仙。广ΤΓ IA丄、， Γ <乱乳％境 上夕， 分鐘(峰值保持時間)後，測定銅粉膜 上之玻璃與銅粉膜間之接 、 糊燒成時之狀態下評價破璃之…b 了於類似於銅導體 玻璃/閏濕性，於本發明中，藉由 該方法測定玻璃料與銅粉之接觸角。 二=:::由如下方式評價玻璃料對氧化銅粉之潤 ”上逑相同之方式’將無玻璃之銅導體糊 128159.doc 17 200903519 絲網印刷於氧化銘基板上，利用⑽之送風乾燥機加執 20分鐘後，代替鳩。C之氮氣環境加熱，而於空氣中^ 230C下保持1G分鐘，分解去除—部分有機㈣，並計 表面被氧化之銅粉膜。並且，以與上述相同之方式，= 破璃料對於該氧化銅粉膜之接觸角。 又，第-玻璃料之軟化點，如上述要件⑴所示 _c以下。若第一玻璃料之軟化點超過_。。，則有 條件下玻璃料之流動性不充分，無法充分潤濕銅粉，=成 所得之銅導體膜之初始密接力下降之虞。第一玻璃料:軟 化點較好的是750以下，推& ^ , 下進而，更好的是700t以下。第 —破璃料之軟化點之下限並無特別設定，但較好的是不比 :導體糊之燒成溫度低3坑以上。若比銅導體糊之燒成 /皿度低350 C以上’則有燒成時玻璃料過於流動，而於燒 成之銅導體財形成較多空隙，導致耐化學藥品性下降2 ^。再者，於存在玻璃之結晶化溫度在玻璃軟化點以上之 並不限制於此’溶融玻璃由於結 降，故可防止過度偏析。 下 如上所述，對銅粉之潤濕性高之第—破璃料，通常耐酸 =充分’僅使用第一玻璃料作為玻璃原料而製備銅導體 '日、’無法獲得具有良好耐電鑛性之銅導體膜。因此，於 發明中，藉由利用使耐酸性等耐化學藥品性高之第二玻 ^與第-玻璃料共存之玻璃料’而表現該兩種玻璃料之 =效果’藉由第—玻璃料可使密接力之提高得以維持， 糟由第二玻璃料可使耐電雜大幅提高。即，將併用第 128159.doc 18 200903519 玻璃料與弟二破 時，第二破璃料師Γ 銅 進行塗佈而燒成 粉表面移動，與2 〃濕性㊅之第—玻璃料所潤濕之銅 臈與基板之結璃料同樣地發揮燒結助劑及銅導體 無較大混合力，以=°又」由於燒成步驟為短時間且 界面相互溶解，亦以〜玻璃料與第二玻璃料既便於接觸 傾斜存在於第—麵料^苐-破璃料 到…* 二玻二:= 二破璃料對銅粉==:二良好之潤濕性，第 料與鋼粉之接觸角，並_ j璃科弟-破璃 為了藉由使用第二破璃料而二…度以下左右即可。 、+, π 增科而獲得良好之耐電鍍性，如μ 組许切 員為1 mgw細下。若第二玻璃料之、、容 —r，則有耐化學藥品性、尤其是二 刀’對丈疋成所得之銅導體膜之保護效果不 錢時銅導體膜之密接力大幅下降之虞。 於電 為了有效㈣如上所述之❹第—與第 璃料所產生的相乘效果，如上述要 兩種玻 之軟化點與第二玻璃料之軟化 坡璃料 朴 π 秋化點之差必須為1 50°C以下。 若軟化點之差超過15(rc且差值變大，則有第一成 璃料於燒成過程中分離，潤濕性不好之第二玻璃料 至所燒成之銅導體膜與基板間的接合層中，體 电㈣下降之虞。卜玻璃料與第二玻璃料之軟化 128159.doc -19- 200903519 點哪個高均可’但較好的是第二玻璃料與第一玻璃料同樣 地亦不比銅導體糊之燒成溫度低35(rc以上。 又’為了併用第一與第二玻璃料而獲得良好之密接力及 耐電鑛性’如上述要件（4)所示，相對於破璃料總量，第一 玻璃料之含量必須為10〜70質量％，第二玻璃料之含量必 ^為：〜：質量％。若第一與第二玻璃料之含量偏離該範 圍，第—破璃料之含量過多，則有耐電鍍性下降之虞， 相反若第二玻璃料之含量過多，則有密接力下降之虞。、 所使用之麵料之粒徑及敎並無特㈣定，較好 粒徑為0.1〜10 pm之範圍。 疋 於本發明巾，較好的是於銅導體财觀氧化銅粉。作 為該氧化銅，可使用Cu2〇或㈤等，該等可單獨使用— 性Μ可將兩種以上併用。由於氧化銅粉與玻璃料之潤渴 良好’因此即便減少第一玻璃料之調配量，亦可確伴； 燒成之銅導體糊之密接力。因此，相對而言，可增 玻璃料之調配量，可確伴密 9 — 之耐化與％ 保在接力’並進一步提高銅導體糊 之4Π:樂―生。5亥氧化銅粉之調配量，相對於100質量 =之銅粉，較好的是㈣質量份之範圍。再者，作為= 銅粉，可調配使用全邻卞 ’、’、乳化 利用於η 僅表面部分被氧化之銅粉，亦可 、土板上印刷.乾燥銅導體糊後 銅粉部分氧化之方法。 乳化步驟而使 氧：銅粉構成導電性粉末之一部分，於調配 夺’破璃㈣對於㈣與氧仙粉 二 質量份之鋼粉盥4各&, 早係相對於 刀〃巩化鋼粉之合計量，較好的是設 128159.doc •20- 200903519 璃料為2〜2〇質量份之範圍’更好的是3〜Η)質量份之範圍。 當然，於未調配氧化銅粉時’相對於1〇〇質量份之鋼粉， 玻璃料為2〜20質量份之笳®。# (靶圍。於破璃料未達2質量份時， 有銅導體膜之而f電鑛性不亦八4 + 『+充刀之虞，於超過20質量份時， 有燒成後之玻璃料析出至銅導體膜之表面，降低電氣特 性、導熱性及焊接性之虞。 又，作為有機媒劑’可使料有機黏合劑溶解於有機溶 劑者。作為有機黏合劑，並益 並，，、、特別限定，可使用燒成過程 中易於被燒毀且灰分少之右擁几人a, 有機化合物，例如聚甲基丙烯酸 丁 S旨、聚曱基丙稀酸甲陆 砰欠T S日荨丙烯酸類，硝化纖維辛、乙美 纖維素、乙酸纖維素、丁基纖維 取乙基 聚喊類，聚丁二烯、聚里戌纖維素類，聚甲酸等 獨佶用錄* 、、戊-烯荨聚乙烯類等，該等可單 獨使用-種，亦可將兩種以上混合使用。 作為有機溶劑，並無特別限定， 適度黏性，且將銅導體糊塗佛…用對銅導體糊賦予 易於被捏…： 板後，藉由乾燥處理而 易於被揮發之有機化合物’例如卡必 松油醇、嶋、二甲基味哇 ％乙以、 甲酼脸 二 唾琳酮、二甲基 尹醯胺、二丙嗣醇、三乙二醇、對土 佛爾鲖等高沸黜古德，々 、乳酸乙酯、異 兩種以上混合使用。 使用-種，亦可將 除調配上述以銅粉為主體之導 媒劑外，亦可視t末、破璃料、有機 祝而要而調配表面活性劑、 由將該等混合而可製備鋼導體糊。各材料：：化劑等，藉 特別限制，相對於⑽質量份之導電性^調配比例並無 々禾，而可於玻璃 128159.doc 200903519 料為2〜20質量份、有機黏 9 # 用兩貝里份、有機溶劑尨 2〜5〇貝量份之範圍内，根攄 為 i + 據所使用之印刷·塗佈方法或所 要未之印刷圖案的精度等進行 斤 糊之製造方法，並i特別^本發明之銅導體 、“ ，、，、特別限定’可使用攪拌器、三輥 ' ㊉ 煉機等，咬者·u 先〜 5專’可根據糊黏度或用途而採用 无刖公知之方法。 上將t此所獲得之本發明之銅導體糊塗佈於耐熱性基板 ，進行燒成，藉此可形成鋼導體膜。銅導體糊之塗佈， I藉由絲網印刷等任意方法進行，又，燒成較好的是㈣ 成溫度為600〜l〇〇(TC(峰值溫度 " )右k成時間為5〜30分 鐘（峰值溫度保持時間）左右之條件下進行。 κ 並且，藉由電路圖案將鋼導體糊塗佈於耐埶性基板上 進行燒成，而利用銅導體臈形成電路，藉此可獲料體電 路板。作為财熱性基板，並無特別限定，為陶究等具有可 承又銅導體糊之燒成溫度之耐熱性電絕緣材料即可。作 耐熱溫度為600t以上之陶瓷材料，例如可列舉：氧化 鋁、氧化錯、氧化鈹、富銘紅柱石、鎮撤禮石、堇青石、 鈦酸錯、《鋇、鈦酸錯酸料氧化物㈣莞，氮化石夕、 氮化銘、碳切等非氧化㈣陶£等。該等之中，氧化銘 及氮化鋁因成本、機械特性、電氣特性 故尤其好。 U生專優異， 又，形成於耐熱性基板上之銅導體膜之厚度，並益特別 限定’可根據印刷·塗佈方法及所要求之用途進行任意設 定。於以一次之塗佈量無法獲得充分之膜厚時，可進:多又 128159.doc •22- 200903519 次重複塗佈以獲得特定之膜厚。於進行多次重複塗佈時， 除使用相同之銅導體糊以外，亦可於塗佈上層日寺，使用其 他糊此時’與耐熱性基板黏接之糊使用本發明之糊因 此"T獲付向禮接力或耐電鍵性。 如上所述，較好的是於利用銅導體膜形成電路所得之導 體電路板中’實施無電解電鍍或電解電鍍，而於銅導體膜 之表面形成金屬鍍層。以此種方式於銅導體膜之表面形成 金屬鎮層’藉此可利用金屬鍍層來防止銅導體膜氧化，可 獲侍阿可罪性且焊接性優異之導體電路板。電鍍法並無特 J限定，可使用公知之電解電鍍法或無電解電鑛法。將本 發月之銅導體糊進行燒成而所得之銅冑體膜緻密且玻璃成 刀之耐酸性咼，因此電鍍後之密接力下降明顯小於由先前 之銅導體糊製造的燒成銅膜。再者，銅及玻璃成分之财酸 生耐鹼性基本上不太高，因此更好的是使用更中性藥 液，選定較短之處理時間進行電鍍。 又’如上所述利用設置於耐熱性基板之銅導體膜形成積 g電奋益等’藉此可利用導體電路板形成電子零件。炎 .再- 於5亥電子零件中’可將銅導體糊進行塗佈.燒成而形 成外。卩電極’並可形成具有外部電極之電子零件。 [實施例] 繼而’藉由實施例具體說明本發明。 (坡璃料） 如表1 所示’準備"1-1”〜，'1-4”、”2-1”〜2-6'，、'，3-1”〜”3_ 3 、”4-1”〜”4_2"之13種玻璃料。 128l59.doc -23 - 200903519 並且，將與未氧化銅粉之接觸角為 4”的玻璃料分類A筮^ 卜之1 I〜I- 、夜…紐 將饥下於10質量％硫酸水溶 : 度41 mgW.hr以下〜”2-6"的玻璃料分 將不適於上述兩者…，〜，一璃料分 頭局弟二組。又 從黎 少 又將弟一組玻璃料與第二組玻璃料，以 1 . 2之質量比率，招入空办以说山 杈入至鉑坩堝中，並於1000〜1250。<：下 :行炼融混合而使成分均句彳匕，使其流入陶竟板上而急速 冷：後，利用球磨機粉碎，將分級所得之均勾化玻璃料設 為第四組。所有玻璃料之平均粒徑為2 〇〜4 〇叫之範圍。 再者，表1中亦揭示有各玻璃料與銅板及氧化銅粉之接 觸角，但可明瞭對銅板或氧化銅粉之接觸角與對未氧化銅 粉之接觸角之間並無明確相關性。 [表1] 分類 第一組 玻璃料 No. 1-1 玻璃之組成系 ZnO-Si02-B2〇3 玻瑤性質 0 軟化點 CO ——-- 10% 硫酸溶解度 (mg/cm2-hr) 接觸角([ 銅板 未氧化 銅粉膜 1~~—'-— 氧化銅 粉膜 632 102.2 7.78 33.9 117 1-2 ZnO-Si02-B2〇3-R2〇 580 100.8 3.3 17.6 i J. / 1 Λ η 1-3 ZnO-Si02-B2〇3-R2〇 535 75,2 24.8 40.0 1\J. / 0 ο 1-4 Zn0-Si02-B203 606 56.0 29.6 30 2 J/ 第二組 第三組 2-1 ZnO-Si02-B2〇3-R20 570 0.0 9.0 74.0 lU 0 1 2-2 Si02-B203-R20 578 0.0 13.5 84.6 15.1 2-3 Si〇2*B2〇3"R2〇 670 0.0 36.9 68.3 47 〇 2-4 Bi203-Si02-B2〇3 690 0.3 60.1 83.4 36 5 2-5 Si02-B203-R'0 775 —— 0.0 74.7 81.2 58.3 2-6 Si02-B203-Zr02-R20 750 0.0 81.5 105.5 63 2 3-1 ZnO-Si02-B2〇3-R20 600 94.0 59.0 89.6 3.8 —---- ΛΠ 1 3-2 ZnO-Si02-B2〇3-R2〇 592 104.8 74.2 80.1 3-3 Zn0-Si02-B203-R20 555 6.0 67.6 79.0 35 i 第四組' 4-1 1-1與2-1之1/2熔融混合物 612 43.6 35.0 78.9 4-2 1-2與2-1之1/2熔融混合物 •— 580 28.2 43.2 76.2 - -24- 128159.doc 200903519 表中之破璃之組成系”中之，,R2〇,%Li2〇、Na2〇、之 總稱的標記。 表中之玻璃之組成系"中之"R，〇”係Mg〇、Ca〇、、 SrO之總稱的標記。 (銅導體糊之製備） 固定銅粉、有機媒劑之調配量，將表丨之玻璃料單獨使 用或以兩種之組合使用，而製備如表2所示之"糊i "〜,m” 之27種調配的銅導體糊。”糊丨，，〜"糊15"係本發明之實施例 之銅導體糊，”糊16”〜"糊27,，係比較例之銅導體糊。 作為銅叙，使用平均粒經為5 之基礎銅粉，及平均粒 徑為1 μΓΠ、平均粒徑為〇·5 μπι、平均粒徑為〇3 μιη之三種 微細助劑銅粉。作為有機媒劑，使用將作為有機黏合劑之 丙烯酸系樹脂溶解於作為溶劑之卡必醇及松油醇者。並 且’使用攪拌器混合各材料後，利用三輥均勻混合，藉此 獲仔銅導體糊。 [表2] 128159.doc 200903519Kj 3 钇 lead-free glass. As the first frit containing no lead and conditions, " Baxi αη AJ ~ from U Sl〇2-B203 Jn〇 is the main zinc bismuth borate glass, with s R, 〇 (R is alkali Metal, R, is 2 2 3 _ 2〇4Si〇2-B2〇3_ 璃. ^ The main component of the oleophthalic acid Boma is due to Zno's improvement with the wetting of copper is included in the first smashing + Therefore, the second glass frit 1 which is better is the above (4) 〇 / and ^ ^^-B2〇3-R2LtSi〇n〇4i^^^^^ which satisfies the above requirements, R, which is the soil for soil examination) Main 2 1 2-B2〇3_R, 0 (R is the gold-cutting granule of the gold-cutting knife, optional I28159.doc 200903519 铋-based glass with BhOrSiO2 as the main component. Furthermore, because 铋 is rare Resources, and the harmful information is still insufficient, so it is better to avoid using it. Here, the glass frit is coated with a copper conductor paste on a substrate to be fired, wetted copper, promoted sintering, and burned. The role of the bonding agent between the copper conductor film and the substrate. That is, if the firing temperature is the softness of the first glass frit, and the first glass frit wets the copper powder and squirts the flow, the steel powder is also reacted with the crucible. mobile When the firing temperature reaches the sintering temperature of the copper powder, the copper # begins to burn, and the copper conductor film obtained by firing under such conditions is dense, and the glass bonding layer is uniformly diffused to the copper conductor film. The high bonding strength of the copper conductor film can be obtained between the substrate and the substrate. If the wettability of the first glass frit is low, the molten glass cannot smoothly move between the copper powders, and cannot function as a sintering aid, and is not sufficient. It functions as a bonding layer between the copper conductor film and the substrate. As a result, the copper conductor film obtained by firing is poor in sintering, the adhesion between the copper conductor film and the substrate is lowered, and the copper conductor is poor in sintering and the density is deteriorated. Therefore, the electro-money liquid in the electric ore is easy to "go to the bonding layer, and the bonding strength of the bonding layer after the electric ore which is infiltrated by the electric ore 9 is greatly low. Therefore, in order to ensure the adhesion of the copper conductor film obtained by coating the copper conductor paste" As shown in the above requirement (1), it is necessary to have a wettability of a contact angle of the first glass frit and the copper powder of 60 degrees or less. In order to obtain a better adhesion, it is more preferable that the contact angle between the glass frit and the copper powder is 45 degrees to The lower the contact angle between the glass frit and the copper powder, the lower the limit is not particularly set. Here, as the evaluation of the wettability of the glass frit to the copper powder in the copper conductor paste, 128l59.doc 16-200903519 It has been proposed to evaluate the shape and surface of the steel powder in the actual copper conductor paste according to the method of the inventors of the present invention. The state is = 2 in the copper plate, the evaluation results of the copper plate do not accurately reflect the wettability of the copper powder in the actual copper conductor paste, and the glass material to the copper powder in the copper conductor paste. The glass evaluation object is directly used by the real p ^ square. That is, as a wetting sputum, the method used in the actual copper conductor paste is similar to the case where the copper conductor paste is fired. The shape of f & the wettability of the glass. First, the same composition as the copper conductor & gate was used to remove only the glass frit to obtain a glass-copper conductor paste. The 25-inch mesh stainless steel wire mesh was used to screen the entire surface of the copper glass conductor paste in 3 inches.忖χ 3 Ying Yu's oxidation on the substrate. Then, use 12 〇, 矣π. The solvent was volatilized by heating in a y k air dryer for 2 minutes, and then, under nitrous oxide, at 300 t for 10 minutes, a part of the organic vehicle was removed to obtain a copper powder film attached to the oxidized substrate. After being covered and processed into a steel film with a diameter of 5 axes and a so-called ancient household, the door is covered with a glass of 5 mm size, and the furnace is used for oxygen concentration. For the next, at 9 sen. ΤΓ ΤΓ 丄 , , , 丄 丄 丄 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱 乱...b is similar to copper conductor glass / wettability, in the present invention, the contact angle of the glass frit with the copper powder is determined by the method. Two =::: The glass frit is evaluated for the run of the copper oxide powder by the following method: The glass-free copper conductor paste 128159.doc 17 200903519 is screen printed on the oxidized substrate and dried by air blowing (10). After the machine is added for 20 minutes, it is heated in the nitrogen atmosphere instead of 鸠C. It is kept in the air for 2G minutes at 230C, and the organic part (4) is decomposed and removed, and the surface is oxidized copper powder film. The method, the contact angle of the glass frit to the copper oxide powder film. Further, the softening point of the first frit is less than _c as shown in the above requirement (1). If the softening point of the first frit exceeds _. Under certain conditions, the fluidity of the glass frit is insufficient, and the copper powder cannot be sufficiently wetted, and the initial adhesion of the obtained copper conductor film is reduced. The first glass frit: the softening point is preferably 750 or less, push & ^ , , Further, more preferably 700t or less. The lower limit of the softening point of the first glass frit is not specifically set, but it is better than: the firing temperature of the conductor paste is lower than 3 pits. Burning paste / low degree of 350 C or more 'when burning The glass material is too fluid, and the copper conductor in the firing forms more voids, resulting in a decrease in chemical resistance. In addition, the presence of the crystallization temperature of the glass above the softening point of the glass is not limited to this melting. Since the glass has a drop, it can prevent excessive segregation. As described above, the first material, which has high wettability to copper powder, is generally resistant to acid = sufficient 'only use the first frit as a glass raw material to prepare a copper conductor'. In the invention, it is not possible to obtain a copper conductor film having good electric ore resistance. Therefore, in the invention, it is expressed by using a glass frit which coexists with a second glass material and a glass frit having high chemical resistance such as acid resistance. The effect of the two kinds of glass frits is that the improvement of the adhesion can be maintained by the first frit, and the resistance of the electric frit can be greatly improved by the second frit. That is, the combination of the 128159.doc 18 200903519 frit and When the second brother breaks, the second glazed Γ copper is coated and the surface of the fired powder moves, and the copper ruthenium wetted by the second 〃 性 第 — 玻璃 玻璃 发挥 发挥 发挥 臈 臈 臈 臈 臈 臈 臈 臈 臈Auxiliaries and copper conductors Large mixing force, = ° and "Because the firing step is short time and the interface dissolves each other, the ~ glass frit and the second glass frit are both easy to contact and the slope exists in the first fabric - 苐 - 破 玻璃料... Glass 2:= Two broken glass to copper powder ==: two good wettability, the contact angle between the first material and the steel powder, and _ j glass brother - broken glass in order to use the second broken glass ... can be around. , +, π Zengke and get good resistance to electroplating, such as μ group of 1⁄4w. If the second glass frit has a capacity of -r, the chemical resistance of the copper conductor film is greatly reduced when the protective effect of the copper conductor film obtained by the second knife is not sufficient. In order to be effective (4) as described above, the effect of multiplication between the first and the third material, as described above, must be the difference between the softening point of the two kinds of glass and the softening slope of the second glass frit. It is below 1 50 °C. If the difference between the softening points exceeds 15 (rc and the difference becomes large, the first glass frit is separated during the firing process, and the second glass frit having poor wettability is transferred between the sintered copper conductor film and the substrate. In the joint layer, the body electricity (four) drops. The softening of the glass frit and the second frit 128159.doc -19- 200903519 whichever height can be 'but preferably the second frit is the same as the first frit The ground is not lower than the firing temperature of the copper conductor paste by 35 (rc or more. Also, in order to use the first and second glass frits to obtain good adhesion and resistance to electric ore, as shown in the above requirement (4), The total amount of glass material, the content of the first glass frit must be 10 to 70% by mass, and the content of the second glass frit must be: ~: mass%. If the content of the first and second glass frits deviates from the range, the first If the content of the glass frit is too large, the plating resistance is lowered. On the contrary, if the content of the second glass frit is too large, the adhesion is lowered. The particle size of the fabric used and the flaw are not specified (4). The preferred particle size is in the range of 0.1 to 10 pm. Copper oxide powder. As the copper oxide, Cu2〇 or (5), etc., which can be used alone, can be used alone or in combination. Since the copper oxide powder and the glass frit are good in thirst, even if the first glass is reduced The blending amount of the material can also be accompanied by the close contact force of the fired copper conductor paste. Therefore, the blending amount of the glass frit can be relatively increased, and it can be confirmed that the heat-resistant and the %-protected in the relay' Further improve the copper conductor paste 4: Le Sheng. 5 Hai copper oxide powder blending amount, relative to 100 mass = copper powder, preferably (four) parts by mass. In addition, as = copper powder, can be adjusted The use of all-neighboring 、', ', emulsification is used for the copper powder whose surface portion is oxidized only by η, or by printing on the soil plate. The copper powder is partially oxidized after drying the copper conductor paste. The emulsification step makes oxygen: copper powder composition One part of the conductive powder, in the blending of the broken glass (four) for (four) and oxygen powder powder of two parts by mass of steel powder 各 4 each &, the early system relative to the total weight of the knife and steel, it is better to set 128159. Doc •20- 200903519 Glass is 2~2〇 parts by mass 'Better is 3 to Η.) The range of parts by mass. Of course, when the copper oxide powder is not blended, the glass frit is 2 to 20 parts by mass relative to 1 part by mass of the steel powder. # (target When the glass frit is less than 2 parts by mass, there is a copper conductor film and the f-minerality is not the same as that of the knives. When it exceeds 20 parts by mass, the glass frit is precipitated after firing. The surface of the copper conductor film is reduced in electrical properties, thermal conductivity, and solderability. Further, as an organic vehicle, an organic binder can be dissolved in an organic solvent. As an organic binder, it is also an organic binder. In particular, it is possible to use a few people who are easily burned and have low ash during the firing process, and an organic compound, such as poly(methacrylic acid), and polymethyl methacrylate, which is owed to TS, acrylic, Nitrocellulose, cyanocellulose, cellulose acetate, butyl fiber, ethyl polyphony, polybutadiene, poly-sodium cellulose, polyformic acid, etc. Ethylene or the like may be used alone or in combination of two or more. The organic solvent is not particularly limited, and it is moderately viscous, and the copper conductor is paste-coated with an organic compound which is easy to be kneaded by a copper conductor paste: a plate which is easily volatilized by a drying process, such as carbene Oleohydrin, hydrazine, dimethyl odor, acetaminophen, acetaminophen, dimethoprim, dipropanol, triethylene glycol, high-boiling gluten , hydrazine, ethyl lactate, or a mixture of two or more. In addition to the use of the above-mentioned copper powder as the main vehicle, the surfactant can also be formulated according to the end of the t, the glass frit, the organic wish, and the steel conductor can be prepared by mixing the same. paste. Each material:: a chemical agent, etc., by special limitation, relative to (10) parts by mass of the conductive ^ compounding ratio is not 々, but can be used in glass 128159.doc 200903519 2~20 parts by mass, organic sticky 9 # with two In the range of 2 to 5 ounces of the content of the berry and the organic solvent ,, the root 摅 is i + according to the printing and coating method used, or the precision of the printing pattern to be used, etc., and i In particular, the copper conductor of the present invention, ",,,, and particularly limited" can be used with a stirrer, a three-roller 'seven refiner, etc., bite · u first ~ 5 special' can be used according to paste viscosity or use. The copper conductor paste of the present invention obtained by applying the copper conductor paste obtained on the heat-resistant substrate is fired to form a steel conductor film. The coating of the copper conductor paste is performed by any method such as screen printing. Further, it is preferable that the firing is performed under the conditions of a temperature of 600 to 1 〇〇 (TC (peak temperature ") and a right k-forming time of 5 to 30 minutes (peak temperature holding time). κ and, Applying a steel conductor paste to a tamper resistant substrate by a circuit pattern In the case of firing, a copper conductor 臈 is used to form a circuit, whereby a bulk circuit board can be obtained. The heat-generating substrate is not particularly limited, and is heat-resistant electrical insulation having a firing temperature of a copper conductor paste such as ceramics. The material can be used as a ceramic material with a heat resistance temperature of 600t or more, for example, alumina, oxidized oxidized, cerium oxide, Fuming andalusite, town reclaimed stone, cordierite, titanic acid, and strontium titanate. Acid oxides (4) Wan, nitrite, nitriding, carbon cutting and other non-oxidation (4) Tao, etc. Among them, Oxidation and aluminum nitride are particularly good due to cost, mechanical properties and electrical properties. In addition, the thickness of the copper conductor film formed on the heat-resistant substrate is particularly limited, and can be arbitrarily set according to the printing and coating method and the intended use. When the film thickness is thick, it can be further: 128159.doc •22- 200903519 Repeat coating to obtain a specific film thickness. When performing repeated coating, in addition to using the same copper conductor paste, it can also be coated. Upper level temple, use other paste When the paste bonded to the heat-resistant substrate is used, the paste of the present invention is used to "receive the bonding force or the electric resistance." As described above, it is preferable to use the copper conductor film to form the circuit in the conductor circuit board. 'Improve electroless plating or electrolytic plating, and form a metal plating on the surface of the copper conductor film. In this way, a metal town layer is formed on the surface of the copper conductor film', thereby preventing the oxidation of the copper conductor film by using the metal plating layer. A conductive circuit board which is sinful and excellent in solderability. The electroplating method is not limited to J, and a known electrolytic plating method or electroless electroforming method can be used. The copper conductor paste of this month is fired. The copper ruthenium film is dense and the glass is chemically resistant to the knives, so the adhesion after plating is significantly reduced compared to the fired copper film produced from the previous copper conductor paste. Furthermore, the acidity and alkali resistance of copper and glass components are not so high, so it is better to use a more neutral liquid and select a shorter treatment time for electroplating. Further, as described above, the copper conductor film provided on the heat-resistant substrate can be used to form an electronic component, whereby the electronic component can be formed by the conductor circuit board. Inflammation. In the -5 Hai electronic parts, the copper conductor paste can be coated and fired to form the outside. The crucible electrode 'and can form an electronic component having an external electrode. [Examples] Next, the present invention will be specifically described by way of examples. (Slope material) As shown in Table 1, 'Preparation "1-1'~, '1-4', '2-1'~2-6',, ',3-1'~'3_3,' 13 kinds of glass frits of 4-1"~"4_2" 128l59.doc -23 - 200903519 And, the glass frit with the contact angle of 4" with the unoxidized copper powder is classified as A 筮 ^ 卜 1 I~I- , Night... New will be hungry in 10% by mass sulfuric acid water: Degree 41 mgW.hr below ~"2-6" The glass frit will not be suitable for the above two...,~, one glass material divided into two groups. From Li Shao and his brother's group of glass frits and the second group of glass frit, in a mass ratio of 1.2, into the empty office to say that the mountain into the platinum crucible, and in the 1000~1250. <: The smelting and mixing are carried out so that the ingredients are all squirmed, and they are poured into the ceramic board and rapidly cooled: after that, they are pulverized by a ball mill, and the averaged glass frit obtained by the classification is set to the fourth group. The diameter is 2 〇~4 The range of squeaking. Furthermore, the contact angle of each glass frit with copper plate and copper oxide powder is also shown in Table 1, but the contact angle of copper plate or copper oxide powder and the unoxidized copper can be clarified. Powder contact angle There is no clear correlation between them. [Table 1] Classification of the first group of frits No. 1-1 Composition of glass ZnO-Si02-B2〇3 Glassy properties 0 Softening point CO ——-- 10% Sulfuric acid solubility (mg /cm2-hr) Contact angle ([ Copper plate unoxidized copper powder film 1~~-'-- Copper oxide powder film 632 102.2 7.78 33.9 117 1-2 ZnO-Si02-B2〇3-R2〇580 100.8 3.3 17.6 i J / 1 Λ η 1-3 ZnO-Si02-B2〇3-R2〇535 75,2 24.8 40.0 1\J. / 0 ο 1-4 Zn0-Si02-B203 606 56.0 29.6 30 2 J/ Group 2 Three groups of 2-1 ZnO-Si02-B2〇3-R20 570 0.0 9.0 74.0 lU 0 1 2-2 Si02-B203-R20 578 0.0 13.5 84.6 15.1 2-3 Si〇2*B2〇3"R2〇670 0.0 36.9 68.3 47 〇2-4 Bi203-Si02-B2〇3 690 0.3 60.1 83.4 36 5 2-5 Si02-B203-R'0 775 —— 0.0 74.7 81.2 58.3 2-6 Si02-B203-Zr02-R20 750 0.0 81.5 105.5 63 2 3-1 ZnO-Si02-B2〇3-R20 600 94.0 59.0 89.6 3.8 —---- ΛΠ 1 3-2 ZnO-Si02-B2〇3-R2〇592 104.8 74.2 80.1 3-3 Zn0-Si02- B203-R20 555 6.0 67.6 79.0 35 i Group 4 '4-1 1-1 and 2-1 1/2 molten mixture 612 43.6 35.0 78.9 4-2 1-2 and 2-1 1/2 melt mixture •— 580 28.2 43.2 76.2 - -24- 128159.doc 200903519 The composition of the broken glass in the table is the general name of R2〇, %Li2〇, Na2〇. The composition of the glass in the table is the general name of Mg 〇, Ca 〇, and SrO. (Preparation of copper conductor paste) The amount of fixed copper powder and organic vehicle will be The glass frit of the watch was used alone or in combination of two, and 27 kinds of copper conductor pastes of the "paste" <~, m" shown in Table 2 were prepared. "Paste," "paste 15" is a copper conductor paste of the embodiment of the present invention, "paste 16" ~ " paste 27, which is a copper conductor paste of a comparative example. As a copper, the average grain size is used. 5 base copper powder, and three kinds of fine auxiliary copper powder with an average particle diameter of 1 μΓΠ, an average particle diameter of 〇·5 μπι, and an average particle diameter of 〇3 μιη. As an organic vehicle, it will be used as an organic binder. The acrylic resin is dissolved in carbitol and terpineol as a solvent, and 'the materials are mixed using a stirrer, and then uniformly mixed by three rolls to obtain a copper conductor paste. [Table 2] 128159.doc 200903519
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vs ®tN 128159.doc -26- 200903519 (實施例1〜8) 使用滿足本發明之（1)〜（4)之要件的"糊】"〜"糊8"之任— 銅導體糊，又，使用3英忖χ3英忖χ〇 635咖厚度之96%氧 化鋁基板（Nikko股份有限公司製造）作為耐熱性基板。 繼而，使用排列多個2 mm x2 mm之圖案而設置之不鏽鋼 絲網#250(線徑為30 μιη、乳劑厚度為1〇 μηι) ’將銅導體糊 絲網印刷於耐熱性基板之表面。繼而，使用l5〇t之送風 乾燥機將該印刷基板乾燥2〇分鐘而去除溶劑後，將印刷基 板放入輸送爐内，於輸送爐内通過6〇分鐘，於空氣中進行 高溫乾燥，從而分解去除—部分有機黏合劑。此時，分別 通過將峰值溫度設為210t：、22(rc、23(rc之輸送爐内於 三種溫度條件下進行乾燥。繼而，將上述乾燥之印刷基板 放入帶式燒成爐内，達到峰值溫度9〇(rc後保持1〇分鐘， 於4條件下，於氧氣濃度為5 ppm以下之氮氣環境中進行 燒成，從而形成銅導體膜。 進而，將如上所述形成銅導體膜之燒成銅膜基板，浸潰 於溫度為4(TC之酸性清洗劑（上村工業公司製造之”acl_ 〇〇7”）180秒鐘後，於濃度為1〇〇 g/L之硫酸水溶液中浸潰 秒鐘，進行表面處理，去除氧化物。繼而，為了使作為無 電解鎳電鍍析出之觸媒的鈀附著於銅導體膜之銅上，而浸 潰於鈀活化劑（上村工業公司製造之"MSR~28。後，進而浸 潰於8CTC之無電解鎳電鍍液（上村工業公司製造之”NpR_ 4”）7分鐘。其後，於15〇Ό下乾燥2〇秒鐘，藉此獲得於銅導 體膜上附著有鎳電鍍膜之導體電路板。 128159.doc -27· 200903519 如下述，對以上述之方式所獲得之導體電路板測定電鍍 前後之銅導體膜與基板之密接力，又，評價燒成條件依賴 性。將結果示於表3。 電鍍前後之銅導體膜與基板之密接力的試驗，係藉由下 述方式進行，將彎曲成L型之直徑為0.6 mm之鍍錫銅線， 焊接固定於2 mm X 2 mm大小的銅導體膜之表面，藉由鐘錫 銅線沿垂直於基板之方向拉伸銅導體膜，使用拉伸試驗機 (西進商事公司製造之”SS15WD”）測定銅導體膜之密接力。 此處，將對220°C下高溫乾燥後所燒成之銅導體膜之測定 結果表示為電鍍前或電鍍後之密接力。 燒成條件依賴性之評價，係對上述220°C下高溫乾燥後 所燒成之銅導體膜之電鍍前密接力，與210°C及230°C下高 溫乾燥後所燒成之銅導體膜之電鍍前密接力進行比較，其 差均為1 0%以下時判定為” 〇 ”，任何一個為1 0%以上且未達 20%時判定為”△”，若任何一個為20%以上，則判定為Vs ® tN 128159.doc -26- 200903519 (Examples 1 to 8) The use of "paste""~" paste 8" which satisfies the requirements of (1) to (4) of the present invention - copper conductor paste Further, a 96-inch alumina substrate (manufactured by Nikko Co., Ltd.) of 3 inches by 3 inches of 635 coffee thickness was used as the heat-resistant substrate. Then, a copper conductor paste was screen-printed on the surface of the heat-resistant substrate by using a stainless steel mesh #250 (wire diameter: 30 μm, emulsion thickness: 1 〇 μηι) provided by arranging a plurality of patterns of 2 mm x 2 mm. Then, the printed circuit board was dried by a blow dryer of 15 〇t for 2 minutes to remove the solvent, and then the printed substrate was placed in a transfer furnace, and dried in the air for 6 minutes in a transfer furnace to be decomposed in the air. Remove - part of the organic binder. At this time, the peak temperature was set to 210t:, 22 (rc, 23 (r) in the transfer furnace to dry under three temperature conditions. Then, the dried printed substrate was placed in a belt firing furnace to reach The peak temperature was 9 Torr (1 sec after rc, and was fired in a nitrogen atmosphere having an oxygen concentration of 5 ppm or less under conditions of 4 to form a copper conductor film. Further, the copper conductor film was formed as described above. The copper-clad substrate was immersed in an aqueous solution of sulfuric acid having a concentration of 1 〇〇g/L for 180 seconds after being immersed in a temperature of 4 (TC acid cleaning agent (acl_ 〇〇7) manufactured by Uemura Industrial Co., Ltd.). In the second, the surface treatment is carried out to remove the oxide. Then, palladium which is a catalyst for electroless nickel plating is attached to the copper of the copper conductor film, and is impregnated with a palladium activator (manufactured by Uemura Industrial Co., Ltd.). After MSR~28, it was further impregnated with 8CTC of electroless nickel plating solution (NpR_4" manufactured by Uemura Industrial Co., Ltd.) for 7 minutes. Thereafter, it was dried at 15 Torr for 2 sec seconds, thereby obtaining copper. Conductor circuit board with nickel plating film attached to the conductor film 128159.doc -27. 200903519 The adhesion of the copper conductor film before and after plating to the substrate was measured for the conductor circuit board obtained as described above, and the firing condition dependency was evaluated. The results are shown in Table 3. The test for the adhesion between the copper conductor film and the substrate before and after electroplating was carried out by soldering a copper wire bent to an L-shaped diameter of 0.6 mm to a copper conductor of 2 mm X 2 mm. On the surface of the film, the copper conductor film was stretched in a direction perpendicular to the substrate by a tin-copper wire, and the adhesion of the copper conductor film was measured using a tensile tester (SS15WD manufactured by Sejin Corporation). The measurement results of the copper conductor film fired after drying at a high temperature of 220 ° C are shown as the adhesion force before or after plating. The evaluation of the firing condition dependence is performed after the high temperature drying at 220 ° C. The pre-plating adhesion of the copper conductor film is compared with the pre-plating adhesion of the copper conductor film fired at 210 ° C and 230 ° C after high-temperature drying. When the difference is less than 10%, it is judged as "〇". Any one is more than 10% and not up to It is judged as "△" at 20%, and if any one is 20% or more, it is judged as
X M CX M C
[表3] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 糊 糊1 糊2 糊3 糊4 糊5 糊6 糊7 糊8 玻璃料1/玻璃料2 1/2 1/2 1/2 1/2 1/2 1/2 1/2 M2 玻璃對銅粉之調配量 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% 玻璃1與玻璃2之軟化點差 62 14 35 36 2 90 110 143 基板 96%氧化鋁基板 電鍍前密接力(kgf) 2.85 2.73 2.88 2.62 2.83 2.44 2.56 2.53 電鍍後密接力(kgf) 2.68 2.46 2.53 2.44 2.61 2.25 2.31 1.98 燒成條件依賴性 〇 〇 〇 〇 〇 〇 〇 △ 如表3所示，實施例1〜8之導體電路板即便於電鍍後亦均 表現良好之密接力。又，即便將高溫乾燥溫度大幅地自 128159.doc -28- 200903519 2 1 0°C變化至230°C，亦無需調整燒成時之氧氣，便可獲得 穩定之密接力，因而燒成條件依賴性較低。 (實施例9〜15) 使用滿足本發明之（1)~(4)之要件的”糊1”〜”糊7”之任一 銅導體糊，又，使用3英吋X 3英吋X 0.63 5 mm厚度之氮化鋁 基板（MARUWA股份有限公司製造）來作為耐熱性基板。 繼而，以與（實施例1〜8)相同之方式，進行銅導體糊之 絲網印刷、南溫乾餘-燒成、無電解電鑛》從而獲得導體 電路板。以與（實施例1〜8)相同之方式，對該導體電路板 測定電鍍前後之銅導體膜與基板之密接力，又，評價燒成 條件依賴性。將結果示於表4。 [表4] 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 實施例15 糊 糊1 糊2 糊3 糊4 糊5 糊6 糊7 玻璃料1/玻璃料2 1/2 1/2 1/2 1/2 1/2 1/2 1/2 玻璃對銅粉之調配量 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% 玻璃1與玻璃2之軟化點差 62 14 35 36 2 90 110 基板 氮化鋁基板 電鍍前密接力(kgf) 2.86 2.69 2.53 2.55 2.56 2.31 2.46 電鍍後密接力(kgi) 2.52 2.11 2.27 2.28 2.34 2.02 2.11 燒成條件依賴性 0 0 〇 〇 〇 0 〇 如表4所示，實施例9〜1 5之導體電路板即便於電鍍後亦 均表現良好之密接力。又，即便將高溫乾燥溫度大幅地自 210°C變化至230°C，亦無需調整燒成時之氧氣，便可獲得 穩定之密接力，因而燒成條件依賴性較低。 如上述實施例1〜1 5所示，可確認不論玻璃料之種類或組 成，併用滿足本發明之（1)〜(4)之要件的兩種玻璃料，藉此 即便於電鍍後亦均表現良好之密接力，可獲得穩定之密接 128159.doc -29- 200903519 力。 (實施例16〜19) 使用改變玻璃料對銅粉之調配量的”糊9”〜’'糊12"之任一 銅導體糊，又，使用96%氧化鋁基板來作為耐熱性基板。 繼而，以與（實施例1〜8)相同之方式，進行銅導體糊之 絲網印刷、尚溫乾舞-燒成、無電解電鍵’從而獲得導體 電路板。以與（實施例1〜8 )相同之方式，對該導體電路板 測定電鍍前後之銅導體膜與基板之密接力，又，評價燒成 條件依賴性。將結果示於表5。 [表5] 實施例16 實施例Π 實施例18 實施例19 糊 糊9 糊10 糊11 糊12 玻璃料1/玻璃料2 1/2 1/2 1/2 1/2 玻璃對銅粉之調配量 6.00% 9.00% 3.00% 2.00% 玻璃1與玻璃2之軟化點差 14 14 14 14 基板 96%氧化鋁基板 電鍍前密接力(kgf) 2.82 3.02 2.36 2.08 電鍍後密接力(kgf) 2.69 2.86 2.08 1.66 燒成條件依賴性 〇 〇 Δ Δ 如表5所示，實施例1 8、19之銅導體糊因玻璃料之調配 量分別少至3.0質量％、2.0質量％，故由於電鍍而導致密接 力稍有下降，電鍍後之密接力稍低於其他實施例，燒成條 件依賴性亦稍有增加，但處於可用之範圍。 (實施例20〜22、比較例1〜3) 使用改變第一玻璃料與第二玻璃料之調配比之”糊 1 3 ”〜π糊1 8”的任一銅導體糊，又，使用96%氧化鋁基板來 作為财熱性基板。 128159.doc •30· 200903519 繼而，以與（實施例1〜8)相同之方式，進行銅導體糊之 絲網印刷、溫乾餘-燒成、無電解電鍵^從而獲得導體 電路板。以與（實施例1〜8)相同之方式，對該導體電路板 測定電鍍前後之銅導體膜與基板之密接力，又，評價燒成 條件依賴性。將結果示於表6。 [表6][Table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Paste 1 Paste 2 Paste 3 Paste 4 Paste 5 Paste 6 Paste 7 Paste 8 Glass frit 1 / frit 2 1/2 1/2 1/2 1/2 1/2 1/2 1/2 1/2 M2 glass to copper powder 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% glass 1 and glass 2 softening point difference 62 14 35 36 2 90 110 143 Substrate 96% alumina substrate pre-plating adhesion (kgf) 2.85 2.73 2.88 2.62 2.83 2.44 2.56 2.53 Post-plating adhesion (kgf) 2.68 2.46 2.53 2.44 2.61 2.25 2.31 1.98 Burning Conditional dependence 〇〇〇〇〇〇〇 Δ As shown in Table 3, the conductor circuit boards of Examples 1 to 8 exhibited good adhesion even after plating. Moreover, even if the high-temperature drying temperature is greatly changed from 128159.doc -28-200903519 2 1 0 °C to 230 ° C, it is not necessary to adjust the oxygen during firing to obtain a stable close contact force, and thus the firing condition depends. Less sexual. (Examples 9 to 15) Any of the copper conductor pastes of "paste 1" to "paste 7" satisfying the requirements of (1) to (4) of the present invention, and 3 inches x 3 inches X 0.63 were used. A 5 mm thick aluminum nitride substrate (manufactured by MARUWA Co., Ltd.) was used as a heat resistant substrate. Then, in the same manner as in (Examples 1 to 8), screen printing of copper conductor paste, south temperature dry-firing, and electroless electrowinning were carried out to obtain a conductor circuit board. In the same manner as in the first to eighth embodiments, the conductor circuit board was measured for the adhesion between the copper conductor film and the substrate before and after the plating, and the firing condition dependency was evaluated. The results are shown in Table 4. [Table 4] Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Paste 1 Paste 2 Paste 3 Paste 4 Paste 5 Paste 6 Paste 7 Glass frit 1 / frit 2 1/2 1 /2 1/2 1/2 1/2 1/2 1/2 glass to copper powder 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% Softening difference between glass 1 and glass 2 62 14 35 36 2 90 110 Substrate adhesion of aluminum nitride substrate before plating (kgf) 2.86 2.69 2.53 2.55 2.56 2.31 2.46 Adhesion after plating (kgi) 2.52 2.11 2.27 2.28 2.34 2.02 2.11 Firing condition dependence 0 0 〇〇〇0 As shown in Table 4, the conductor circuit boards of Examples 9 to 15 exhibited good adhesion even after plating. Further, even if the high-temperature drying temperature is largely changed from 210 ° C to 230 ° C, it is not necessary to adjust the oxygen at the time of firing, and a stable adhesive force can be obtained, so that the firing condition dependency is low. As shown in the above Examples 1 to 15, it was confirmed that the two types of glass frits satisfying the requirements of (1) to (4) of the present invention were used regardless of the type or composition of the glass frit, thereby exhibiting even after plating. Good close contact, you can get a stable close connection 128159.doc -29- 200903519 force. (Examples 16 to 19) A copper conductor paste of any of "paste 9" to "paste 12" which changed the amount of the glass frit to the copper powder was used, and a 96% alumina substrate was used as the heat resistant substrate. Then, in the same manner as in (Examples 1 to 8), a copper conductor paste was subjected to screen printing, dry-drying-baking, and electroless-free bonding to obtain a conductor circuit board. In the same manner as in the first to eighth embodiments, the conductor circuit board was measured for the adhesion between the copper conductor film and the substrate before and after the plating, and the firing condition dependency was evaluated. The results are shown in Table 5. [Table 5] Example 16 Example 实施 Example 18 Example 19 Paste 9 Paste 10 Paste 11 Paste 12 Glass frit 1 / frit 2 1/2 1/2 1/2 1/2 Glass to copper powder 6.00% 9.00% 3.00% 2.00% Softening difference between glass 1 and glass 2 14 14 14 14 Substrate 96% alumina substrate before plating (kgf) 2.82 3.02 2.36 2.08 Post-plating adhesion (kgf) 2.69 2.86 2.08 1.66 Burning Conditional dependence 〇〇Δ Δ As shown in Table 5, the copper conductor pastes of Examples 18 and 19 were reduced to 3.0% by mass and 2.0% by mass, respectively, so that the adhesion was slightly caused by electroplating. The adhesion after plating was slightly lower than that of the other examples, and the firing condition dependency was slightly increased, but it was in a usable range. (Examples 20 to 22, Comparative Examples 1 to 3) Using any of the copper conductor pastes which changed the mixing ratio of the first glass frit and the second glass frit, "paste 1 3" to π paste 1 8", and used 96 again. The % alumina substrate is used as a heat-generating substrate. 128159.doc • 30· 200903519 Then, in the same manner as (Examples 1 to 8), the copper conductor paste is screen-printed, dried, dried, and electroless. The conductor circuit board was obtained by the electric key. The adhesion of the copper conductor film before and after the plating to the substrate was measured for the conductor circuit board in the same manner as in the first to eighth embodiments, and the firing condition dependency was evaluated. Shown in Table 6. [Table 6]
實施例 20 實施例 21 實施例 22 比較例1 比較例2 比較例3 糊 糊13 糊14 糊15 糊16* 糊17* 糊18* 玻璃料1/玻璃料2 1/3 1/1 2/1 3/1 1/0 0/1 玻璃對銅粉之調配量 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% 玻璃1與玻璃2之軟化點差 14 14 14 14 / / 基板 96%氧化鋁基板 電鍍前密接力(kgf) 2.42 2.68 2.64 2.72 2.46 2.17 電鍍後密接力(kgi) 2.37 2.12 1.88 1,35 0.88 1.68 燒成條件依賴性 〇 〇 〇 〇 〇 X 如表6所示，含有第一玻璃料之調配量為75質量％之”糊 1 6”的比較例1、或含有第一玻璃料之調配量為1 00質量％之 "糊1 7 ”的比較例2，耐酸性不充分且由於電鍍而導致密接 力大幅下降。又，僅使用耐酸性高之第二玻璃料之'’糊18” 的比較例3，電鍍前之初始密接力低，並且電鍍後之密接 力亦大幅下降，進而受燒成條件之影響亦大。另一方面， 第一玻璃料與第二玻璃料之質量比率處於1/3〜2/1之範圍的 實施例20〜22，表現良好之耐電鍍性及燒成條件低依賴 性。 (比較例4〜5 ) 使用第一玻璃料與第二玻璃料之軟化點之差為1 50°C以 128159.doc •31 - 200903519 上的”糊19”、"糊20”之任一銅導體糊，又，使用96%氧化 鋁基板來作為耐熱性基板。 繼而，以與（實施例1〜8)相同之方式，進行銅導體糊之 絲網印刷、高溫乾燥-燒成、無電解電鍍，從而獲得導體 電路板。以與（實施例1〜8)相同之方式，對該導體電路板 測定電鍍前後之銅導體膜與基板之密接力，又，評價燒成 條件依賴性。將結果示於表7。 [表7] 比較例4 比較例5 糊 糊19* 糊20* 玻璃料1/玻璃料2 1/1 1/1 玻璃對銅粉之調配量 4.50% 4.50% 玻璃1與玻璃2之軟化點差 195 170 基板 96%氧化鋁基板 電鍍前密接力(kgf) 2.49 2.42 電鍍後密接力(kgf) 1.52 1.44 燒成條件依賴性 Δ Δ 如表7所示，電鍍前之初始密接力良好，但電鍍後之密 接力大幅下降，耐電鍍性不充分。又，燒成條件依賴性亦 稍有增加。推測其原因在於：兩種玻璃料之軟化點之差較 大，玻璃料相互分離而無法發揮相乘效果。 (比較例6〜1 0) 使用未併用第一玻璃料與第二玻璃料之’’糊21”〜”糊25” 之任一銅導體糊，又，使用96%氧化鋁基板來作為耐熱性 基板。 繼而，以與（實施例1〜8)相同之方式，進行銅導體糊之 絲網印刷、南溫乾無-燒成、無電解電鑛^從而獲得導體 128159.doc -32- 200903519 電路板。以與（實施例1〜8)相同之方式，對該導體電路板 測定電鍍前後之銅導體膜與基板之密接力，又，評價燒成 條件依賴性。將結果示於表8。 [表8] 比較例6 比較例7 比較例8 比較例9 比較例10 糊 糊21* 糊25* 糊22* 糊24* 糊23* 玻璃料1/玻璃料2 1/1 1/1 1/1 1/1 1/1 玻璃對銅粉之調配量 4.50% 4.50% 4.50% 4.50% 4.50% 玻璃1與玻璃2之軟化點差 52 8 30 14 25 基板 96%氧化鋁基板 電鍍前密接力(kgf) 2.67 2.32 2.23 2.08 2.48 電鍍後密接力(kgf) 1.07 1.47 1.55 1.64 1.26 燒成條件依賴性 △ X X X △ 如表8所示，耐電鍍性及燒成條件依賴性均差於實施 例。 (比較例11〜12) 並非使用分別將第一玻璃料與第二玻璃料調配至糊中所 得者，而是使用利用作為該等之熔融混合物之玻璃料”4-1” 或”4-2”所製備的”糊26”、”糊27”之任一銅導體糊，又，使 用96%氧化鋁基板來作為耐熱性基板。 繼而，以與（實施例1〜8)相同之方式，進行銅導體糊之 絲網印刷、兩溫乾舞-燒成、無電解電鍵5從而獲得導體 電路板。以與（實施例1〜8)相同之方式，對該導體電路板 測定電鍍前後之銅導體膜與基板之密接力，又，評價燒成 條件依賴性。將結果示於表9。 128159.doc -33 - 200903519 [表9] 比較例11 比較例12 糊 糊26* 糊27* 玻璃料1/玻璃料2 1/1** 1/1** 玻璃對銅粉之調配量 4.50% 4.50% 玻璃1與玻璃2之軟化點差 / / 基板 96%氧化鋁基板 電鍍前密接力(kgi) 2.03 1.98 電鍍後密接力(kgf) 1.12 1.29 燒成條件依賴性 X X :並非使用將兩種玻璃料併用調配者，而是使用預先進行熔融混合者 如表9所示，第一玻璃料與第二玻璃料之兩種玻璃料之 炫融混合品，對銅粉之潤濕性差，财酸性亦差，因此均不 屬於第一或第二之任一組（參照表1)。因此，如表9所示， 所得之導體電路板之銅導體膜的密接性、耐電鍍性、及燒 成條件依賴性均差。若將該結果與實施例1、2之結果進行 比較，則可明瞭併用本發明之第一玻璃料與第二玻璃料之 兩種玻璃料的相乘效果。 128159.doc -34-Example 20 Example 21 Example 22 Comparative Example 1 Comparative Example 2 Comparative Example 3 Paste 13 Paste 14 Paste 15 Paste 16* Paste 17* Paste 18* Glass frit 1 / frit 2 1/3 1/1 2/1 3 /1 1/0 0/1 Glass to copper powder 4.50% 4.50% 4.50% 4.50% 4.50% 4.50% Softening difference between glass 1 and glass 2 14 14 14 14 / / Substrate 96% alumina substrate before plating Bonding force (kgf) 2.42 2.68 2.64 2.72 2.46 2.17 Bonding force after plating (kgi) 2.37 2.12 1.88 1,35 0.88 1.68 Firing condition dependence 〇〇〇〇〇X As shown in Table 6, containing the first frit Comparative Example 1 in which the amount of "paste 16" of the amount of 75% by mass or the comparative example 2 of the "paste 1 7" containing the first glass frit was 100% by mass, the acid resistance was insufficient and due to electroplating As a result, the adhesion is greatly reduced. In addition, in Comparative Example 3 in which only the second glass frit of the acid resistance is used, the initial adhesion before plating is low, and the adhesion after plating is also greatly lowered, and then burned. The impact of the conditions is also large. On the other hand, in Examples 20 to 22 in which the mass ratio of the first glass frit to the second glass frit was in the range of 1/3 to 2/1, the electroplating resistance and the firing conditions were excellent in dependence. (Comparative Examples 4 to 5) The difference between the softening point of the first glass frit and the second glass frit was 1500 ° C to any of "paste 19" and "paste 20" on 128159.doc • 31 - 200903519 A copper conductor paste was further used as a heat-resistant substrate by using a 96% alumina substrate. Then, screen printing, high-temperature drying-baking, and electroless plating of a copper conductor paste were carried out in the same manner as in (Examples 1 to 8). Electroplating was carried out to obtain a conductor circuit board. The conductor board was measured for the adhesion between the copper conductor film and the substrate before and after plating, and the firing condition dependency was evaluated in the same manner as in (Examples 1 to 8). Table 7: Comparative Example 4 Comparative Example 5 Paste 19* Paste 20* Glass frit 1 / frit 2 1/1 1/1 Glass to copper powder 4.50% 4.50% Glass 1 and glass 2 Softening point difference 195 170 Substrate 96% alumina substrate pre-plating adhesion (kgf) 2.49 2.42 Electroplating adhesion (kgf) 1.52 1.44 Firing condition dependence Δ Δ As shown in Table 7, the initial adhesion is good before plating However, the adhesion after electroplating is greatly reduced, and the electroplating resistance is insufficient. The reason is also slightly increased. It is presumed that the reason is that the difference between the softening points of the two glass frits is large, and the glass frit is separated from each other and cannot be multiplied. (Comparative Examples 6 to 1 0) The first frit is used in combination. A copper conductor paste of any of the "batter 21" to "paste 25" of the second glass frit was used, and a 96% alumina substrate was used as the heat resistant substrate. Then, in the same manner as in (Examples 1 to 8), a copper conductor paste screen printing, a south temperature dry-free firing, and an electroless electrowinning were carried out to obtain a conductor 128159.doc-32-200903519 circuit board. In the same manner as in the first to eighth embodiments, the conductor circuit board was measured for the adhesion between the copper conductor film and the substrate before and after the plating, and the firing condition dependency was evaluated. The results are shown in Table 8. [Table 8] Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Paste 21* Paste 25* Paste 22* Paste 24* Paste 23* Glass frit 1/Frit 2 1/1 1/1 1/1 1/1 1/1 Glass to copper powder 4.50% 4.50% 4.50% 4.50% 4.50% Softening difference between glass 1 and glass 2 52 8 30 14 25 Substrate 96% alumina substrate before plating (kgf) 2.67 2.32 2.23 2.08 2.48 Contact strength after plating (kgf) 1.07 1.47 1.55 1.64 1.26 Firing condition dependency Δ XXX Δ As shown in Table 8, the plating resistance and the firing condition dependency were all inferior to the examples. (Comparative Examples 11 to 12) Instead of using the first glass frit and the second glass frit to be blended into the paste, respectively, the glass frit "4-1" or "4-2" which is used as the molten mixture is used. A copper conductor paste of any of the prepared pastes 26" and "pastes 27" was used as a heat-resistant substrate by using a 96% alumina substrate. Then, in the same manner as in (Examples 1 to 8), screen printing of the copper conductor paste, two-time dry-drying-baking, and electroless-free key 5 were carried out to obtain a conductor circuit board. In the same manner as in the first to eighth embodiments, the conductor circuit board was measured for the adhesion between the copper conductor film and the substrate before and after the plating, and the firing condition dependency was evaluated. The results are shown in Table 9. 128159.doc -33 - 200903519 [Table 9] Comparative Example 11 Comparative Example 12 Paste 26* Paste 27* Glass frit 1 / frit 2 1/1** 1/1** Glass to copper powder 4.50% 4.50 % Softening difference between glass 1 and glass 2 / / 96% alumina substrate before plating (kgi) 2.03 1.98 Contact strength after plating (kgf) 1.12 1.29 Burning condition dependence XX: Not using two kinds of glass frit In combination with the blender, the melt blending of the first frit and the second frit is shown in Table 9. The wettability of the copper powder is poor, and the acidity is also poor. Therefore, none of them belong to any of the first or second groups (refer to Table 1). Therefore, as shown in Table 9, the copper conductor film of the obtained conductor circuit board was inferior in adhesion, plating resistance, and firing condition dependency. When this result is compared with the results of Examples 1 and 2, the synergistic effect of the two kinds of glass frits of the first glass frit of the present invention and the second glass frit can be clarified. 128159.doc -34-
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| US9799421B2 (en) | 2013-06-07 | 2017-10-24 | Heraeus Precious Metals North America Conshohocken Llc | Thick print copper pastes for aluminum nitride substrates |
| TWI772671B (en) * | 2018-08-23 | 2022-08-01 | 日商昭榮化學工業股份有限公司 | Conductive paste for forming external electrode of multilayer ceramic electronic component |
| TWI786109B (en) * | 2017-04-28 | 2022-12-11 | 日商住友金屬鑛山股份有限公司 | Conductive composition, manufacturing method of conductor, and forming method of wiring of electronic parts |
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| RU2014122255A (en) * | 2011-11-03 | 2015-12-10 | Керамтек Гмбх | AIN BROADCAST BOARDS |
| AT512041B1 (en) * | 2012-05-04 | 2013-05-15 | Mikroelektronik Ges Mit Beschraenkter Haftung Ab | Method for producing a metallized substrate |
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| CN110942840A (en) * | 2019-12-13 | 2020-03-31 | 新昌中国计量大学企业创新研究院有限公司 | Lead-free copper conductor paste for aluminum nitride substrate |
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| TWI786109B (en) * | 2017-04-28 | 2022-12-11 | 日商住友金屬鑛山股份有限公司 | Conductive composition, manufacturing method of conductor, and forming method of wiring of electronic parts |
| TWI772671B (en) * | 2018-08-23 | 2022-08-01 | 日商昭榮化學工業股份有限公司 | Conductive paste for forming external electrode of multilayer ceramic electronic component |
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