JP2012052181A - Copper powder for conductive paste for external electrode excellent in oxidation resistance, and copper paste - Google Patents
Copper powder for conductive paste for external electrode excellent in oxidation resistance, and copper paste Download PDFInfo
- Publication number
- JP2012052181A JP2012052181A JP2010195027A JP2010195027A JP2012052181A JP 2012052181 A JP2012052181 A JP 2012052181A JP 2010195027 A JP2010195027 A JP 2010195027A JP 2010195027 A JP2010195027 A JP 2010195027A JP 2012052181 A JP2012052181 A JP 2012052181A
- Authority
- JP
- Japan
- Prior art keywords
- copper powder
- copper
- tertiary amine
- powder
- conductive paste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000010949 copper Substances 0.000 title claims abstract description 69
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 62
- 230000003647 oxidation Effects 0.000 title claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 23
- 239000004793 Polystyrene Substances 0.000 claims abstract description 60
- 229920002223 polystyrene Polymers 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 6
- 230000002411 adverse Effects 0.000 abstract description 3
- 239000003985 ceramic capacitor Substances 0.000 description 40
- 239000000203 mixture Substances 0.000 description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- 238000009413 insulation Methods 0.000 description 21
- 238000005245 sintering Methods 0.000 description 20
- 238000005259 measurement Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 7
- 239000005751 Copper oxide Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910000431 copper oxide Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- KMVWNDHKTPHDMT-UHFFFAOYSA-N 2,4,6-tripyridin-2-yl-1,3,5-triazine Chemical compound N1=CC=CC=C1C1=NC(C=2N=CC=CC=2)=NC(C=2N=CC=CC=2)=N1 KMVWNDHKTPHDMT-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 2
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 2
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- -1 hydrazine compound Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- SHPQVJNNBXMZRW-UHFFFAOYSA-N 6-butyldec-5-en-5-yltin Chemical compound CCCCC([Sn])=C(CCCC)CCCC SHPQVJNNBXMZRW-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 241001424392 Lucia limbaria Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 229910007472 ZnO—B2O3—SiO2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009692 water atomization Methods 0.000 description 1
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
本発明は、外部電極用導電性ペースト用銅粉に関し、特に積層セラミックコンデンサや積層セラミックインダクタなどの積層セラミック電子部品の外部電極を形成するための導電性ペーストに使用する銅粉に関するものである。 The present invention relates to copper powder for conductive paste for external electrodes, and more particularly to copper powder used for conductive paste for forming external electrodes of multilayer ceramic electronic components such as multilayer ceramic capacitors and multilayer ceramic inductors.
積層セラミックコンデンサの一般的な製造方法は、まず、チタン酸バリウム系セラミックなどの誘電体セラミックグリーンシートを複数枚用意し、各々のシートの上に、内部電極用の導電性ペーストを所定のパターンで印刷し、これらのシートを積み重ねて圧着することによって、誘電体セラミックグリーンシートと導電性ペースト層が交互に積層された積層体を作製する。この積層体を所定の形状の複数のチップに切断した後、高温で同時に焼成して、積層セラミックコンデンサの素体を作製する。 A general method for manufacturing a multilayer ceramic capacitor is to first prepare a plurality of dielectric ceramic green sheets such as barium titanate-based ceramics, and on each sheet, a conductive paste for internal electrodes in a predetermined pattern. By printing and stacking and pressing these sheets, a laminated body in which dielectric ceramic green sheets and conductive paste layers are alternately laminated is produced. The multilayer body is cut into a plurality of chips having a predetermined shape and then simultaneously fired at a high temperature to produce a multilayer ceramic capacitor element body.
次いで、この素体の内部電極が露出する端面に、導電性粉体、ガラス粉末および有機ビヒクルを主成分とする外部電極用の導電性銅ペーストを塗布し、乾燥した後、高温で焼成することによって外部電極を形成する。その後、必要に応じて外部電極にニッケルやスズなどのめっき層を電気めっきなどにより形成する。 Next, a conductive copper paste for an external electrode mainly composed of conductive powder, glass powder and organic vehicle is applied to the end face where the internal electrode of the element body is exposed, dried, and then fired at a high temperature. To form an external electrode. Thereafter, if necessary, a plating layer of nickel, tin, or the like is formed on the external electrode by electroplating or the like.
ここで使用される外部電極用導電性銅ペーストは、一般には樹脂系バインダーと溶媒からなるビヒクル中にフィラーとして導電性の粉体（導電フィラーと呼ぶ）である銅粉を分散させた流動性のある流体を指し、これを適当な温度に昇温したときにビヒクルが蒸発・分解し、残った導電フィラーが焼結体となって電気の良導体が形成されるものを言う。 The conductive copper paste for external electrodes used here is generally a fluidity in which copper powder, which is a conductive powder (referred to as a conductive filler), is dispersed as a filler in a vehicle composed of a resin binder and a solvent. This refers to a fluid that evaporates and decomposes when the temperature is raised to an appropriate temperature, and the remaining conductive filler becomes a sintered body to form a good electrical conductor.
その実際の使用にあたっては、基板の表面や内部の孔に、このような導電ペーストを塗布または充填した状態で基板と共に適切な加熱処理が行なわれ、この加熱処理によってビヒクルが蒸発・分解・燃焼して除去され、導電フィラーとしての銅粉が互いに焼結して通電可能な回路が形成される。積層セラミックスコンデンサーの場合にも、多数のセラミックス基板の間に内部電極用の導電ペーストを介在させ、またそれらの内部電極間を連結する外部電極用の導電ペーストを塗布し、同様に加熱処理を行い、ビヒクルが蒸発・分解されて除去されて金属粉が焼結し、内部電極および外部電極が形成される。そのさい内部電極と外部電極は別々に焼成されるのが一般的である。 In actual use, an appropriate heat treatment is carried out together with the substrate in such a state that such conductive paste is applied or filled on the surface of the substrate or in the internal holes, and the vehicle evaporates, decomposes and burns by this heat treatment. The copper powder as the conductive filler is sintered to form a circuit that can be energized. In the case of multilayer ceramic capacitors, a conductive paste for internal electrodes is interposed between a number of ceramic substrates, and a conductive paste for external electrodes that connects these internal electrodes is applied, and heat treatment is performed in the same manner. The vehicle is evaporated and decomposed and removed to sinter the metal powder, thereby forming an internal electrode and an external electrode. At that time, the internal electrode and the external electrode are generally fired separately.
従来、積層セラミックコンデンサなどの内部電極を形成するための導電性ペーストに使用する金属材料として、パラジウム、銀−パラジウム、白金などが使用されていたが、これらは高価な貴金属であるため、コストがかかるという問題があった。そのため、近年では、ニッケルや銅などの卑金属を使用するのが主流になってきており、現在では、内部電極には主にニッケル微粒子（積層セラミックコンデンサの大きさや容量などにもよるが、一般に平均粒径０．１〜０．５μｍのニッケル微粒子）が使用されている。また、銅は、導電率が高く、融点が低いため、積層セラミックコンデンサの焼成時の低温化などの生産時の省エネに寄与することが可能であり、外部電極用の金属材料として使用されている。 Conventionally, palladium, silver-palladium, platinum, and the like have been used as metal materials used for conductive pastes for forming internal electrodes such as multilayer ceramic capacitors. However, these are expensive noble metals, and thus cost is low. There was a problem that it took. Therefore, in recent years, the use of base metals such as nickel and copper has become the mainstream, and at present, nickel fine particles (generally depending on the size and capacity of the multilayer ceramic capacitor, etc.) Nickel fine particles having a particle diameter of 0.1 to 0.5 μm are used. In addition, copper has high conductivity and low melting point, so it can contribute to energy saving during production such as low temperature when firing multilayer ceramic capacitors, and is used as a metal material for external electrodes .
しかし、銅粉は通常空気中において表面が酸化され、この酸化物が不動態性を示さず不安定なため、さらに酸化が進行し、導電性が低下する性質を有している。したがってプリント基板などのための印刷用インキ、合成樹脂などに配合して導電性を得るために、従来からこの目的のための銅粉に対して種々の表面処理方法あるいは添加剤の検討がなされている。例えば、銅粉の防錆のための表面処理方法としては、ベンゾトリアゾール、トリルトリアゾールなどによる処理が提案されている（例えば、日刊工業新聞社刊「防錆技術便覧」参照）が、これらの処理により得られる保護皮膜は、銅粉の変色防止効果は認められるが、導電性ペースト用銅粉の導電性を著しく低下させるために、銅粉の表面処理剤としては使用不可能である。 However, the surface of copper powder is usually oxidized in the air, and since this oxide does not show passivity and is unstable, the oxidation further proceeds and the conductivity is lowered. Therefore, various surface treatment methods or additives have been conventionally studied for copper powder for this purpose in order to obtain conductivity by blending with printing inks for printed boards, synthetic resins, etc. Yes. For example, as a surface treatment method for rust prevention of copper powder, treatment with benzotriazole, tolyltriazole, etc. has been proposed (for example, refer to “Handbook of Rust Prevention Technology” published by Nikkan Kogyo Shimbun). Although the protective film obtained by the above method has an effect of preventing discoloration of copper powder, it cannot be used as a surface treatment agent for copper powder because the conductivity of the copper powder for conductive paste is remarkably lowered.
また、導電性を低下させない方法として、特許文献１及び２では原料である水酸化銅から還元剤を用いて金属銅粒子に還元する際に、還元剤としてヒドラジンまたはヒドラジン化合物を使用する手法であり、製法が限定される。 In addition, as a method for not lowering the conductivity, Patent Documents 1 and 2 are methods in which hydrazine or a hydrazine compound is used as a reducing agent when reducing the raw material copper hydroxide to metallic copper particles using a reducing agent. The production method is limited.
さらに特許文献３においては、水溶性の有機溶媒中で、銅粉，オルガノシラン化合物および水を反応させてオルガノシランの加水分解生成物を生成させ，得られた懸濁液にゲル化剤を添加して銅粉にゲルコーティング膜を被着させる手法が挙げられているが、溶液の調整や膜厚の均一化には手間がかかる。 Furthermore, in Patent Document 3, a hydrolyzed product of organosilane is produced by reacting copper powder, an organosilane compound and water in a water-soluble organic solvent, and a gelling agent is added to the resulting suspension. Although a technique for depositing a gel coating film on copper powder is mentioned, it takes time to adjust the solution and make the film thickness uniform.
一方、特許文献４および５には、銅ペースト組成物にホウ酸及びホウ素を添加することが記載されている。しかしながら、吸湿性の強いホウ酸やホウ素を外部電極用銅ペースト組成物中に添加すると、そのペースト中に微量に存在する水分や、外気の湿度の影響を受け、ペースト中に分散したホウ酸やホウ素が、吸湿や潮解を起こし、ペーストの粘度の安定性が劣り、粘度が大きく経時変化するという問題がある。 On the other hand, Patent Documents 4 and 5 describe that boric acid and boron are added to a copper paste composition. However, when boric acid or boron, which has high hygroscopicity, is added to the copper paste composition for external electrodes, boric acid dispersed in the paste is affected by moisture present in the paste and the humidity of the outside air. Boron causes moisture absorption and deliquescence, and there is a problem that the viscosity of the paste is inferior and the viscosity greatly changes with time.
本発明は、上述のような従来技術の有する問題を解消するために成されたもので、電気的特性への悪影響を回避しながら、従来の導電性ペースト用銅粉より更に耐酸化性、高い初期導電率及び耐湿性を有する導電性ペースト用銅粉を提供するものである。 The present invention was made to solve the above-mentioned problems of the prior art, and has higher oxidation resistance and higher resistance than conventional copper powder for conductive paste while avoiding adverse effects on electrical characteristics. The present invention provides a copper powder for conductive paste having initial conductivity and moisture resistance.
本発明者らは、上記課題を解決するために鋭意研究した結果、下記の化学式１で示される３級アミン置換ポリスチレンを被覆することで、高い耐酸化性を有する銅粉及び、電気的特性への悪影響を回避する銅ペーストを安定して製造することができることを見出し、本発明を完成するに至ったものである。 As a result of diligent research to solve the above-mentioned problems, the present inventors have coated a tertiary amine-substituted polystyrene represented by the following chemical formula 1 to achieve high oxidation resistance copper powder and electrical characteristics. The present inventors have found that a copper paste that avoids the adverse effects of can be stably produced, and have completed the present invention.
本発明に係る第一の発明は、耐酸化性に優れた外部電極用導電性ペースト用銅粉が下記の化学式１に示す３級アミンを有する重量平均分子量２０００〜２０００００のポリマーがコーティング膜として銅粉の表面を被覆していることを特徴とする。 According to the first aspect of the present invention, a copper powder for an external electrode conductive paste excellent in oxidation resistance has a tertiary amine represented by the following chemical formula 1 and has a weight average molecular weight of 2000 to 200000 as a coating film. It is characterized by covering the surface of the powder.
また、本発明に係る第２の発明は、耐酸化性に優れた外部電極用導電ペースト用銅粉が、外部電極用導電性ペースト用銅粉の粒径が球状粉の場合では平均粒径１μｍ以上１０μｍ以下、あるいは鱗片粉の場合では平均粒径が３μｍ以上、４０μｍ以下であり、化学式２で示す３級アミン置換ポリスチレン（重量平均分子量２０００〜２０００００）のコーティング膜が形成されていることを特徴とする。 In addition, the second invention according to the present invention is such that the copper powder for conductive paste for external electrodes having excellent oxidation resistance is an average particle diameter of 1 μm when the particle size of the copper powder for conductive paste for external electrodes is a spherical powder. 10 μm or less, or in the case of scale powder, the average particle diameter is 3 μm or more and 40 μm or less, and a coating film of tertiary amine-substituted polystyrene (weight average molecular weight 2000 to 200000) represented by Chemical Formula 2 is formed. And
さらに、本発明にかかる第３の発明は、耐酸化性に優れた外部電極用導電性ペースト用銅粉が、球状または鱗片状の形状を有することを特徴とし、第４の発明は、外部電極用銅ペーストが、前記外部電極用導電性ペースト用銅粉が樹脂系バインダーと溶媒とからなるビヒクルに分散していることを特徴とする。 Furthermore, the third invention according to the present invention is characterized in that the copper powder for conductive paste for an external electrode excellent in oxidation resistance has a spherical or scaly shape, and the fourth invention is an external electrode. The copper paste for conductive material is characterized in that the copper powder for conductive paste for external electrodes is dispersed in a vehicle composed of a resin binder and a solvent.
なお、銅粉の導電性を損なうことなく被覆可能な材料としては、導電性ポリマーが挙げられるが、剛直な特性を持つためにその柔軟性が悪く、銅粉の表面を均一に被覆することができないため、酸化抑制効果がなかった。また合成難度も高いという課題もある。 In addition, as a material that can be coated without impairing the conductivity of the copper powder, a conductive polymer can be cited. However, since it has a rigid characteristic, its flexibility is poor and the surface of the copper powder can be uniformly coated. Since it was not possible, there was no oxidation suppression effect. There is also a problem that the synthesis difficulty is high.
一般的なコーティング材料であるシリコンポリマーは、容易に銅粉を被覆できるために、酸化抑制効果はあるものの、導電性を持たないことから、銅粉の導電性を著しく低下させる。
一方、化学式１で示される３級アミン置換ポリスチレンは、対応する３級アミン置換スチレンモノマーから合成され、分子量が大きく得られるために薄膜で均一なコーティング膜を欠損なく銅粉に被覆させることが可能である。
また、化学式１で示される３級アミン置換ポリスチレンの３級アミン部位によって半導体特性が付与されており、形成されたコーティング膜は銅粉の導電性を損なうことがない。
また、化学式１で示される３級アミン置換ポリスチレンのポリスチレン骨格に基づき、高いガスバリア性及び撥水効果を付与させることが可能となり、被覆された銅粉は高温高湿条件下にて高い酸化抑制機能を持つ。
Since silicon polymer, which is a general coating material, can be easily coated with copper powder, it has an oxidation-inhibiting effect, but does not have conductivity, so that the conductivity of copper powder is significantly reduced.
On the other hand, the tertiary amine-substituted polystyrene represented by Chemical Formula 1 is synthesized from the corresponding tertiary amine-substituted styrene monomer and has a large molecular weight, so a thin and uniform coating film can be coated with copper powder without defects. It is.
Moreover, the semiconductor characteristic is provided by the tertiary amine site | part of the tertiary amine substituted polystyrene shown by Chemical formula 1, and the formed coating film does not impair the electroconductivity of copper powder.
Moreover, based on the polystyrene skeleton of tertiary amine substituted polystyrene represented by Chemical Formula 1, it becomes possible to impart high gas barrier properties and water repellency, and the coated copper powder has a high oxidation-inhibiting function under high temperature and high humidity conditions. have.
さらに、銅粉へのコーティング手法には、３級アミン置換ポリスチレンをハロゲン系炭化水素、トルエン、テトラヒドロフラン、アルコール類に溶解させ、特に制限はないが湿式法、スプレー法を用いてよい。 Further, as a method for coating copper powder, tertiary amine-substituted polystyrene is dissolved in halogenated hydrocarbon, toluene, tetrahydrofuran, and alcohols, and there is no particular limitation, but a wet method or a spray method may be used.
この銅粉は、例えば平均粒径が１０μｍ以下の銅粉の粒子表面に０．５μｍ以下の厚みの３級アミン置換ポリスチレンが形成されているものであり、銅粒子は形状を問わず、球状のものであるほか鱗片状の形状を有することもできる。さらに本発明の銅ペースト組成物は、主として３級アミン置換ポリスチレンによるコーティング膜をもつ耐酸化性に優れた銅粉、およびガラス質フリットと有機ビヒクルとから構成されている。 In this copper powder, for example, a tertiary amine-substituted polystyrene having a thickness of 0.5 μm or less is formed on the surface of a copper powder particle having an average particle size of 10 μm or less. It can also have a flaky shape. Furthermore, the copper paste composition of the present invention is mainly composed of copper powder having a coating film made of tertiary amine-substituted polystyrene and excellent in oxidation resistance, a glassy frit and an organic vehicle.
本発明によれば、銅粉の耐酸化性を著しく高めることができるようになり、その結果、導電ペーストのフィラーに使用した場合、その焼結過程での脱バインダー工程での銅粉の酸化を防止できるようになった。これにより、酸化した銅粉を還元する工程が不要となり、導電性ペーストの焼成工程が簡略化できる。
さらに、本発明の外部電極用銅ペースト組成物を用いることによって、内部電極と外部電極の接続性を確保し、積層セラミックコンデンサとしての電気特性、特に容量特性に優れ、信頼性に優れた積層セラミックコンデンサを得ることができる。
According to the present invention, the oxidation resistance of copper powder can be remarkably increased. As a result, when used as a filler for conductive paste, the copper powder is oxidized in the binder removal step during the sintering process. It became possible to prevent. Thereby, the process of reducing the oxidized copper powder becomes unnecessary, and the baking process of the conductive paste can be simplified.
Furthermore, by using the copper paste composition for an external electrode of the present invention, the connectivity between the internal electrode and the external electrode is ensured, and the multilayer ceramic capacitor has excellent electrical characteristics, particularly capacity characteristics, and excellent reliability. A capacitor can be obtained.
以下、本発明を詳細に説明する。
（１）３級アミン置換ポリスチレン
本発明のポリマーは、３級アミンを置換したポリスチレンで重量平均分子量が２０００〜２０００００であることを特徴とするが、例えば、ハロゲン置換芳香族化合物とアミン置換芳香族化合物のカップリング反応により２級アミンとし、ｐ−ブロモスチレンとのカップリング反応により得られたモノマー２（化学式３）を重合することで３級アミン置換ポリスチレン（化学式２）を得ることができる。
この合成の際のカップリング反応は、パラジウム触媒を用いたものやウルマン反応、スティルカップリング反応等が望ましいが、特にこれらに限定されない。また、重合反応はラジカル重合が簡便かつ重合度高くポリマーが得られるが、アニオン重合等でも可能である。また、合成経路として、３級アミン合成後にウィティッヒ反応やヘック反応等によりビニル基を構築しモノマーとする経路なども適用できる。
重量平均分子量が２０００未満の場合、銅粉全表面にコーティング膜を形成させることが難しく、重量平均分子量が２０００００を超えると溶媒とする有機溶剤が限定される為好ましくない。
Hereinafter, the present invention will be described in detail.
(1) Tertiary amine-substituted polystyrene The polymer of the present invention is a polystyrene substituted with a tertiary amine and has a weight average molecular weight of 2,000 to 200,000. For example, a halogen-substituted aromatic compound and an amine-substituted aromatic A tertiary amine substituted polystyrene (Chemical Formula 2) can be obtained by polymerizing the monomer 2 (Chemical Formula 3) obtained by the coupling reaction with p-bromostyrene by converting the compound to a secondary amine.
The coupling reaction in this synthesis is preferably a palladium catalyst, Ullmann reaction, Stille coupling reaction, etc., but is not particularly limited thereto. In addition, the polymerization reaction is simple in radical polymerization and a polymer can be obtained with a high degree of polymerization, but anionic polymerization or the like is also possible. In addition, as a synthetic route, a route in which a vinyl group is constructed by using a Wittig reaction, a Heck reaction, or the like after synthesis of a tertiary amine can be used.
When the weight average molecular weight is less than 2000, it is difficult to form a coating film on the entire surface of the copper powder, and when the weight average molecular weight exceeds 200000, the organic solvent used as a solvent is limited, which is not preferable.
（２）銅粉
本発明に用いる銅粉の形状は、特に制限されず、鱗片状または球状の銅粉、あるいは混合して使用することができる。
本発明に用いられる銅粉の製造方法としては、湿式還元法、乾式法等、特に限定はしないが、好ましくは、乾式法の一種である水アトマイズ法によって得られる銅粉を用いるのが良い。この製法は、コスト面で他の製法に比較してより安価に製造できるためである。同様に、鱗片状の銅粉についても、アトマイズ粉を元粉とし、これに、一般的に鱗片粉末を得る方法、例えば、機械的粉砕、圧延等により鱗片化することにより得られる。
外部電極用銅ペースト組成物に用いられる鱗片状銅粉としては、扁平長粒径が３〜３０μｍ程度の粒径が、球状の銅粉としては１〜４μｍの平均粒径が、好適に使用することができる。
(2) Copper powder The shape of the copper powder used in the present invention is not particularly limited, and it can be used as a scaly or spherical copper powder, or as a mixture.
The method for producing the copper powder used in the present invention is not particularly limited, such as a wet reduction method and a dry method, but preferably a copper powder obtained by a water atomization method which is a kind of dry method is used. This is because this manufacturing method can be manufactured at a lower cost than other manufacturing methods in terms of cost. Similarly, the scale-like copper powder can be obtained by using atomized powder as a base powder, and generally scaling it by a method of obtaining scale powder, for example, mechanical pulverization, rolling or the like.
As the scaly copper powder used in the copper paste composition for an external electrode, a particle diameter having a flat long particle diameter of about 3 to 30 μm and an average particle diameter of 1 to 4 μm as a spherical copper powder are preferably used. be able to.
鱗片状の銅粉は、粘性の調整や、外部電極用銅ペースト組成物の焼結後に、積層体のエッジ部分（肩の部分）が切れてしまうエッジ切れを防止するために添加する場合があるが、鱗片状の銅粉の扁平長粒径が３μｍ未満では、エッジ切れ抑制の効果が小さくなり、４０μｍを超えると、焼結膜の平滑性が損なわれ、銅粉の焼結性遅延により、焼結面にポアが生じ、めっき液の侵入を引き起こすことがある。 The scale-like copper powder may be added to prevent edge breakage that causes the edge part (shoulder part) of the laminate to break after adjustment of the viscosity or sintering of the copper paste composition for external electrodes. However, when the flat and long particle diameter of the scaly copper powder is less than 3 μm, the effect of suppressing edge breakage is reduced, and when it exceeds 40 μm, the smoothness of the sintered film is impaired, and the sintering of the copper powder causes a delay in sintering. Pore may be generated on the bonding surface, which may cause penetration of the plating solution.
球状の銅粉の場合、その平均粒径が１μｍ未満では、銅粉が酸化されやすくなり、これに起因して銅の酸化による焼結不良、容量不足、または、ペースト粘度の経時変化が起こりやすくなる。一方、平均粒径が１０μｍを超えると、銅粉の焼結の進行が遅くなり、通常の焼結温度、すなわち９００℃の温度では十分に焼結が進行しないために、焼結面にポアが生じたり、後工程におけるめっき工程で、めっき液の外部電極内への侵入を引き起こしたりすることがある。 In the case of spherical copper powder, if the average particle size is less than 1 μm, the copper powder is likely to be oxidized, and due to this, poor sintering due to copper oxidation, insufficient capacity, or change in paste viscosity over time is likely to occur. Become. On the other hand, if the average particle size exceeds 10 μm, the progress of the sintering of the copper powder becomes slow, and the sintering does not proceed sufficiently at the normal sintering temperature, that is, the temperature of 900 ° C. In some cases, the plating solution may cause penetration of the plating solution into the external electrode during the subsequent plating step.
銅粉の粒径としては、鱗片状または球状で、粒径が小さいほど焼結が進みやすくなる傾向があることを加味し、外部電極用銅ペースト組成物の焼結温度やチップサイズに応じて、粒径や、鱗片状と球状の混合比を最適化して使用することができる。 The particle size of the copper powder is in the form of scales or spheres, taking into account that the smaller the particle size, the easier the sintering proceeds, and depending on the sintering temperature and chip size of the copper paste composition for external electrodes The particle size and the mixture ratio of flaky and spherical shapes can be optimized and used.
銅粉に対して２質量％以上５質量％以下の本発明の３級アミン置換ポリスチレンを溶解させた有機溶媒、例えばハロゲン系炭化水素、アルコール類、テトラヒドロフランに、湿式法の場合は銅粉を入れて２分以上撹拌、浸漬させた後、溶媒を除去して目的とするコーティング膜を有する銅粉を得る。溶媒を除去する工程は特に制限されないが、コーティング膜形成前に銅粉が酸化されることを避ける為に減圧下で除去されることが望ましい。 Put the copper powder in the case of a wet method in an organic solvent in which the tertiary amine-substituted polystyrene of the present invention is dissolved in an amount of 2% by mass to 5% by mass with respect to the copper powder. After stirring and soaking for 2 minutes or longer, the solvent is removed to obtain a copper powder having a desired coating film. The process for removing the solvent is not particularly limited, but it is desirable to remove the solvent under reduced pressure in order to avoid oxidation of the copper powder before forming the coating film.
（３）ガラス質フリット
本発明に用いるガラス質フリットとしては、特に制限されず、外部電極用銅ペースト組成物に一般的に使用されるガラス質フリットを好適に使用できる。例えば、平均粒径１〜６μｍで、軟化点が６００〜８００℃のホウ珪酸ガラス（ＳｉＯ２−Ｂ２Ｏ３系）、ホウ珪酸バリウムガラス（ＢａＯ−ＳｉＯ２−Ｂ２Ｏ３系）等の無鉛ガラス質フリットを挙げることができる。
(3) Glassy frit The glassy frit used in the present invention is not particularly limited, and a glassy frit generally used for a copper paste composition for external electrodes can be suitably used. For example, borosilicate glass (SiO 2 —B 2 O 3 system), borosilicate glass (BaO—SiO 2 —B 2 O 3 system) having an average particle diameter of 1 to 6 μm and a softening point of 600 to 800 ° C. Mention may be made of lead-free glassy frit.
そのガラス質フリットの添加量は、外部電極の焼結温度と、使用する銅粉の粒径とによって、最適量とすることが望ましい。たとえば、焼結温度が高くなるほど、また、銅紛の粒径の小さなガラス質フリットを用いるほど、外部電極は緻密化し、ガラス質フリットが外部電極の表面に押し出される傾向にあるため、これを抑えるには、ガラス質フリットの添加量を減らすことが有効である。
実際には、銅粉に対して、１．５質量％以上１４質量％以下の範囲で調節するのが望ましい。１．５質量％未満であると、前記積層体と外部電極との接着強度が弱くなり、また、１４質量％を超えると、焼結後にガラスが押し出されて外部電極の表面をガラスが覆う状態となり、めっき付き性が悪くなる。
The addition amount of the glassy frit is desirably an optimum amount depending on the sintering temperature of the external electrode and the particle size of the copper powder to be used. For example, the higher the sintering temperature and the smaller the vitreous frit with a small copper powder particle size, the more the external electrode becomes denser and the vitreous frit tends to be pushed out to the surface of the external electrode. It is effective to reduce the amount of glassy frit added.
Actually, it is desirable to adjust the copper powder in the range of 1.5 mass% or more and 14 mass% or less. When the content is less than 1.5% by mass, the adhesive strength between the laminate and the external electrode is weakened. When the content exceeds 14% by mass, the glass is extruded after the sintering and covers the surface of the external electrode. As a result, the plating property deteriorates.
（４）有機ビヒクル
本発明において使用する有機ビヒクルは、特に制限されず、一般的に外部電極用銅ペースト組成物に使用されているものでよい。
例示すれば、樹脂成分としてアクリル樹脂やセルロース樹脂を、溶剤としてはターピネオールやジヒドロターピネオール等のテルペン系溶剤、エチルカルビトール、ブチルカルビトール等のエーテル系溶剤を、単独または複数、混合して使用できる。有機ビヒクルの使用量としては、外部電極用銅ペースト組成物に適度な粘性および塗布性が得られれば良く、例えば、銅粉に対して、１〜５０質量％である。
(4) Organic vehicle The organic vehicle used in the present invention is not particularly limited, and may be one generally used in a copper paste composition for external electrodes.
For example, an acrylic resin or cellulose resin can be used as a resin component, a terpene solvent such as terpineol or dihydroterpineol, or an ether solvent such as ethyl carbitol or butyl carbitol as a solvent can be used alone or in combination. . The amount of the organic vehicle used is only required to obtain an appropriate viscosity and applicability for the copper paste composition for external electrodes, and is, for example, 1 to 50% by mass with respect to the copper powder.
（５）焼結プロセスにおける銅粉の酸化の評価
本発明者らは、焼結プロセスにおける銅粉の酸化が、内部電極と外部電極との接続性に影響を及ぼしているものと考え、本発明の３級アミン置換ポリスチレンがコーティング膜として銅の酸化抑制に与える効果についても検証した。
そこで、アルミナ基板に、銅粉と、ガラス質フリットと、有機ビヒクルとからなる外部電極用銅ペースト組成物を印刷して、乾燥したものを試料とし、酸化銅が生成するかを確認する実験を行った。ピーク温度９００℃のプロファイルにおいて、焼成途中における炉内温度が４５０℃、５５０℃、６５０℃、８００℃の各温度に達した時点で酸化されないように試料を炉からサンプリングして、各温度で酸化銅がどれだけ生成しているかを確認した。
(5) Evaluation of copper powder oxidation in sintering process The present inventors consider that the oxidation of copper powder in the sintering process affects the connectivity between the internal electrode and the external electrode. The effect of the tertiary amine-substituted polystyrene on the suppression of copper oxidation as a coating film was also verified.
Therefore, an experiment was performed to print copper paste composition for external electrodes made of copper powder, glassy frit, and organic vehicle on an alumina substrate, and use the dried one as a sample to check whether copper oxide is produced. went. In the profile with a peak temperature of 900 ° C, the sample was sampled from the furnace so that it was not oxidized when the furnace temperature during firing reached 450 ° C, 550 ° C, 650 ° C, and 800 ° C. It was confirmed how much copper was formed.
酸化銅の生成量は、参考文献（特開２０００−２８０２４８号公報）に記載されている測定方法に従って求めた。すなわち、前記条件で焼結およびサンプリングされた焼結基板をＸＲＤ回折し、Ｃｕメインピーク（２θ＝５０．４度）、酸化銅Ｃｕ２Ｏメインピーク（２θ＝３６．４度）に着目し、そのピークカウント数を比較することで、各温度で酸化銅がどれだけ生成しているかを調べた。
未処理の銅粉を原料とした場合、３級アミン置換ポリスチレンと同様に導電性を持つ低分子化合物を銅粉に被覆させた場合、本発明の３級アミン置換ポリスチレンを被覆させた銅粉を原料とした場合について、それらを使用した外部電極用銅ペースト組成物を作製し、４５０℃、５５０℃、６５０℃、８００℃、９００℃での焼結におけるＣｕピーク及び酸化銅Ｃｕ２Ｏのピークを比較した。
The amount of copper oxide produced was determined according to the measurement method described in the reference (Japanese Patent Laid-Open No. 2000-280248). That is, XRD diffraction is performed on the sintered substrate sampled and sampled under the above conditions, and attention is paid to the Cu main peak (2θ = 50.4 degrees) and the copper oxide Cu 2 O main peak (2θ = 36.4 degrees). By comparing the peak count numbers, it was examined how much copper oxide was generated at each temperature.
When untreated copper powder is used as a raw material, copper powder coated with the tertiary amine-substituted polystyrene of the present invention is coated with a low-molecular compound having conductivity similar to the tertiary amine-substituted polystyrene. About the case where it was made into a raw material, the copper paste composition for external electrodes using them was produced, and the Cu peak and the peak of copper oxide Cu 2 O in sintering at 450 ° C., 550 ° C., 650 ° C., 800 ° C., and 900 ° C. Compared.
その結果、未処理の銅粉を原料とした銅ペースト組成物では５５０℃、６５０℃、８００℃のサンプルでは、酸化銅ピークが検出されたのに対し、導電性低分子化合物を被覆した銅粉は５５０℃、６５０℃、８００℃で比較的弱いが酸化銅ピークが検出された。一方、３級アミン置換ポリスチレンを被覆させた銅粉を原料とした銅ペースト組成物ではまったく検出されなかった。 As a result, in the copper paste composition using untreated copper powder as a raw material, the copper oxide peak was detected in the samples at 550 ° C., 650 ° C., and 800 ° C., whereas the copper powder coated with the conductive low molecular weight compound was used. Was relatively weak at 550 ° C., 650 ° C. and 800 ° C., but a copper oxide peak was detected. On the other hand, it was not detected at all in the copper paste composition using copper powder coated with tertiary amine-substituted polystyrene as a raw material.
一般的に、外部電極用銅ペースト組成物の銅粉が酸化される温度域は約６００〜６５０℃付近であり、外部電極の銅と内部電極のニッケルの焼結にともなう合金化がまだ進行していない温度域では、銅の酸化が徐々に進行してしまうものと考えられる。
また、導電性低分子化合物を被覆した銅粉の場合、均一なコーティング層を形成することが困難な為、完全に銅粉表面を被覆できず部分的に金属銅表面が剥き出しとなり酸化された部分があったと考えられる。
Generally, the temperature range in which the copper powder of the external electrode copper paste composition is oxidized is about 600 to 650 ° C., and the alloying associated with sintering of the external electrode copper and the internal electrode nickel still proceeds. It is considered that the oxidation of copper proceeds gradually in the temperature range where the temperature is not.
Also, in the case of copper powder coated with a conductive low molecular weight compound, it is difficult to form a uniform coating layer, so the copper powder surface cannot be completely covered and the metal copper surface is partially exposed and oxidized It is thought that there was.
本発明の３級アミンを有する重量平均分子量２０００〜２０００００の３級アミン置換ポリスチレンが被覆された銅粉を用いた場合、表層の均一なコーティング膜により銅の酸化は抑制され、結果として良好な導電性が維持され、銅ペースト組成物焼結後の積層セラミックコンデンサの容量も容量設計値に達する結果になるものと考えられる。 When copper powder coated with tertiary amine-substituted polystyrene having a tertiary amine having a tertiary amine of the present invention and coated with tertiary amine-substituted polystyrene is used, copper oxidation is suppressed by a uniform coating film on the surface layer, resulting in good conductivity. It is considered that the capacity of the multilayer ceramic capacitor after sintering the copper paste composition reaches the designed capacity value.
以上によって、本発明の３級アミンを有する重量平均分子量２０００〜２０００００の３級アミン置換ポリスチレンを被覆した銅粉を使用した外部電極用銅ペースト組成物では、ニッケル内部電極との焼結が、銅粉の酸化よりも先に進行し、その結果として、接続をより強固なものにしているものと考えられる。 As described above, in the copper paste composition for an external electrode using the copper powder coated with the tertiary amine-substituted polystyrene having the tertiary amine of the present invention having a weight average molecular weight of 2000 to 200000, the sintering with the nickel internal electrode is performed using copper. It is considered that the process proceeds before the oxidation of the powder, and as a result, the connection is made stronger.
次に、本発明について実施例を用いて説明するが、本発明はこれらの実施例によって何ら限定されるものではない。先ず、実施例で用いた３級アミン置換ポリスチレンについて示す。
（１）３級アミン置換ポリスチレンの合成
以下で説明する合成手法によって、４−ブロモアニソールとｐ−アニシジンを原料として、３級アミン置換ポリスチレンを作製した。なお、合成手法は、以下の方法に限定されるものではない。
Next, although this invention is demonstrated using an Example, this invention is not limited at all by these Examples. First, it shows about the tertiary amine substituted polystyrene used in the Example.
(1) Synthesis of tertiary amine-substituted polystyrene Tertiary amine-substituted polystyrene was prepared from 4-bromoanisole and p-anisidine as raw materials by the synthesis method described below. Note that the synthesis method is not limited to the following method.
［化合物３（化学式４）の合成］
出発原料の４−ブロモアニソール：１５ｇと、ｐ−アニシジン：２０ｇとをトルエン：７０ｍｌに溶解させ、ＢＩＮＡＰ（２，２’−ビスジフェニルフォスフィノ−１，１’−ビナフチル：３．４ｇ、トリス（ジベンジリデンアセトン）ジパラジウム（０）：１．８ｇ、ナトリウム−ｔｅｒｔ−ブトキシド：２２ｇを加え、９５℃で５時間反応させ、精製により下記化学式４に示される化合物３を得た。
[Synthesis of Compound 3 (Chemical Formula 4)]
Starting materials 4-bromoanisole: 15 g and p-anisidine: 20 g were dissolved in 70 ml of toluene, and BINAP (2,2′-bisdiphenylphosphino-1,1′-binaphthyl: 3.4 g, tris ( Dibenzylideneacetone) dipalladium (0): 1.8 g and sodium-tert-butoxide: 22 g were added and reacted at 95 ° C. for 5 hours. Purification gave compound 3 represented by the following chemical formula 4.
［化合物４（化学式５）の合成］
得られた化合物３：２ｇをトルエン：３０ｍｌに溶解させ、１−ブロモ−４−ヨードベンゼン：２．７ｇ、ヨウ化銅（I）：０．７ｇ、ナトリウム−ｔｅｒｔ-ブトキシド：１３ｇ、２，２−ビピリジン：０．３ｇを加え、９５℃で７時間反応させ、精製により下記化学式５に示す化合物４を得た。
[Synthesis of Compound 4 (Chemical Formula 5)]
The resulting compound 3: 2 g was dissolved in toluene: 30 ml, 1-bromo-4-iodobenzene: 2.7 g, copper (I) iodide: 0.7 g, sodium-tert-butoxide: 13 g, 2,2 -Bipyridine: 0.3g was added, it was made to react at 95 degreeC for 7 hours, and the compound 4 shown to following Chemical formula 5 was obtained by refinement | purification.
［モノマー２の合成］
得られた化合物４：８７０ｍｇをトルエン：１０ｍｌに溶解させ、テトラキストリフェニルホスフィンパラジウム（０）：８ｇ、トリ−ｎ−ブチルビニルスズ：１０．８ｇ、ジブチルヒドロキシトルエン：２５１ｇを加え、９５℃で７時間反応させ、精製によりモノマー２を得た。
また、他の方法として、得られた化合物３：２ｇをトルエン：３０ｍｌに溶解し、p-ブロモスチレン：１．２５ ｍｌ、ヨウ化銅(I)：０．７ｇ、ナトリウム−ｔｅｒｔ−ブトキシド：１３ｇおよび２−ビピリジン：０．３ｇを加え、４０℃で暗所にて２４時間反応させ、精製によりモノマー２を得た。
[Synthesis of Monomer 2]
Compound 870 mg obtained was dissolved in 10 ml of toluene, tetrakistriphenylphosphine palladium (0): 8 g, tri-n-butylvinyltin: 10.8 g, dibutylhydroxytoluene: 251 g were added, The reaction was performed for a period of time, and monomer 2 was obtained by purification.
As another method, the compound 3: 2 g obtained is dissolved in 30 ml of toluene, p-bromostyrene: 1.25 ml, copper (I) iodide: 0.7 g, sodium tert-butoxide: 13 g And 2-bipyridine: 0.3 g was added and reacted at 40 ° C. in the dark for 24 hours, and the monomer 2 was obtained by purification.
［３級アミン置換ポリスチレンの合成］
得られたモノマー２：４２ｍｇに、ラジカル反応開始剤としてＡＩＢＮ（α，α'−アゾビスイソブチロニトリル）を添加し、窒素雰囲気下にて６０−７０℃で撹拌して３級アミン置換ポリスチレンを合成した。
[Synthesis of tertiary amine-substituted polystyrene]
AIBN (α, α′-azobisisobutyronitrile) as a radical reaction initiator was added to the obtained monomer 2:42 mg, and the mixture was stirred at 60-70 ° C. in a nitrogen atmosphere to give a tertiary amine-substituted polystyrene. Was synthesized.
ところで、モノマーにおける反応点数に、分子鎖の延長しやすさが依存するため、ここでは、ＡＩＢＮの添加量を０．０５Ｍ（試料５）、０．１Ｍ（試料１）、０．２Ｍ（試料２）、０．５Ｍ（試料３）、１．０Ｍ（試料４）の５水準として、試料１〜５（本発明の範囲内は試料１〜３、範囲外は試料４〜５）の３級アミン置換ポリスチレンを作製した。 By the way, since the ease of extension of the molecular chain depends on the number of reaction points in the monomer, the amount of AIBN added here is 0.05M (sample 5), 0.1M (sample 1), 0.2M (sample 2). ), 0.5M (sample 3), and 1.0M (sample 4) as five levels, tertiary amines of samples 1 to 5 (samples 1 to 3 are within the scope of the present invention, and samples 4 to 5 are outside the range) A substituted polystyrene was prepared.
その作製した５水準の３級アミン置換ポリスチレンの分子量を、ゲル浸透クロマトグラフィー（東ソー株式会社製ＧＰＣ−８０２０）にて重量平均分子量を測定し、大気中光電子分光装置（理研計測株式会社製ＡＣ―２）にて得られたイオン化ポテンシャルの結果から導電性の有無を判定した。その測定結果を表１に示す。
試料１〜５の３級アミン置換ポリスチレンは、いずれも良好な導電性を示していた。
The molecular weight of the five-level tertiary amine-substituted polystyrene prepared was measured by gel permeation chromatography (GPC-8020 manufactured by Tosoh Corporation), and the photoelectron spectrometer in the atmosphere (AC- The presence or absence of conductivity was determined from the result of the ionization potential obtained in 2). The measurement results are shown in Table 1.
All of the tertiary amine-substituted polystyrenes of Samples 1 to 5 showed good conductivity.
（２）銅粉への被覆
（１）で作製した試料１〜５の各３級アミン置換ポリスチレンを、それぞれ銅粉に対して所定量を溶解させたテトラヒドロフラン溶液に、鱗片状銅粉末（福田金属箔粉工業製、品番３Ｌ３、平均粒径１３．１μｍ）あるいは球状銅粉末（日本アトマイズ加工（株）製、品番ＨＸＲ−Ｃｕ、粒径１μｍ）を浸積して形成した溶液を５分間撹拌した後に、銅粉をろ過により分離し、真空条件下で乾燥させて試料１〜５の各３級アミン置換ポリスチレンで被覆した鱗片状銅粉末、球状銅粉末を作製した。
(2) Covering copper powder In a tetrahydrofuran solution in which a predetermined amount of each tertiary amine-substituted polystyrene of Samples 1 to 5 prepared in (1) was dissolved in copper powder, scaly copper powder (Fukuda Metals) Foil powder industry, product number 3L3, average particle size of 13.1 μm) or spherical copper powder (manufactured by Nippon Atomizing Co., Ltd., product number HXR-Cu, particle size of 1 μm) was soaked for 5 minutes. Later, the copper powder was separated by filtration, dried under vacuum conditions, and a scaly copper powder and a spherical copper powder coated with each tertiary amine-substituted polystyrene of Samples 1 to 5 were produced.
（３）有機ビヒクルの作製
配合比率を、ターピネオール７３質量％に、エチルセルロース１質量％、アクリル樹脂２６質量％とし、全量を軽く分散させた後、エアーモーターで撹拌しながら６０℃まで加熱し透明で粘稠な有機ビヒクルを作製した。
(3) Preparation of organic vehicle The blending ratio was 73% by mass of terpineol, 1% by mass of ethyl cellulose and 26% by mass of acrylic resin. The whole amount was lightly dispersed, and then heated to 60 ° C. with stirring by an air motor. A viscous organic vehicle was prepared.
（４）外部電極用銅ペースト組成物の作製
前工程の（２）銅粉への被覆により作製した被覆された銅粉を用いて、この銅粉１００重量部に対し、ホウ珪酸バリウムガラス質フリット（ＢａＯ−ＳｉＯ２−Ｂ２Ｏ３系、軟化点７３０℃）４．５重量部、ホウ珪酸亜鉛ガラス質フリット（ＺｎＯ−Ｂ２Ｏ３−ＳｉＯ２系、軟化点５７０℃）０．５重量部、および（３）で作製した有機ビヒクル３５重量部を秤量し、これらを全量ミキサーで混合した後、更に三本ロールミルによって混練して、外部電極用銅ペースト組成物を作製した。
(4) Preparation of copper paste composition for external electrode Using the coated copper powder prepared by coating (2) copper powder in the previous step, with respect to 100 parts by weight of this copper powder, barium borosilicate glassy frit 4.5 parts by weight (BaO—SiO 2 —B 2 O 3 system, softening point 730 ° C.), 0.5 wt% zinc borosilicate glassy frit (ZnO—B 2 O 3 —SiO 2 system, softening point 570 ° C.) And 35 parts by weight of the organic vehicle prepared in (3) were weighed, and all of these were mixed by a mixer, and then kneaded by a three-roll mill to prepare a copper paste composition for external electrodes.
（５）焼結による試料の作製
従来技術と同様にして、設計静電容量が１μＦとなる積層体を形成し、ニッケル製内部電極の露出した端面に（４）で作製した外部電極用銅ペースト組成物を塗布し、１２０℃で乾燥した後、窒素雰囲気のベルト炉で、ピーク温度９００℃、炉入り口から出口まで６０分のプロファイルで焼成して、特性評価用の試料を作製した。
(5) Preparation of sample by sintering In the same manner as in the prior art, a laminate having a design capacitance of 1 μF was formed, and the external electrode copper paste prepared in (4) on the exposed end face of the nickel internal electrode The composition was applied, dried at 120 ° C., and then fired in a belt furnace in a nitrogen atmosphere with a peak temperature of 900 ° C. and a profile of 60 minutes from the furnace inlet to the outlet to prepare a sample for characteristic evaluation.
［内部電極との絶縁抵抗の評価］
（ａ）静電容量
それぞれの組成の外部電極用銅ペースト組成物を焼き付けて得た銅外部電極に、ニッケルめっきを施して、積層セラミックコンデンサを作製した。
その積層セラミックコンデンサの静電容量を、ＬＣＲメータ（ヒューレットパッカード社製、型式４２７８Ａ）にて測定した。測定周波数は１ｋＨｚで、設計静電容量の１μＦに対し、測定された静電容量が０．９μＦ以上のものを「○」、０．９μＦ未満のものを「×」と評価した。
[Evaluation of insulation resistance with internal electrode]
(A) Capacitance Capacitor external electrodes obtained by baking the copper paste compositions for external electrodes having the respective compositions were plated with nickel to produce multilayer ceramic capacitors.
The capacitance of the multilayer ceramic capacitor was measured with an LCR meter (manufactured by Hewlett-Packard Company, model 4278A). The measurement frequency was 1 kHz, and with respect to the designed capacitance of 1 μF, the measured capacitance was evaluated as “◯” when the measured capacitance was 0.9 μF or more, and “x” when the measured capacitance was less than 0.9 μF.
（ｂ）絶縁抵抗
作製した積層セラミックコンデンサの絶縁抵抗を、高抵抗計（ヒューレットパッカード社製、型式４３２９Ａ）にて測定した。
また、６０℃、９５％ＲＨの高温高湿条件下に５００時間放置した後、再度測定を行った。なお、測定電圧は５０Ｖで、絶縁抵抗が１×１０９以上のものを「○」、１×１０９未満のものを「×」とした。
(B) Insulation Resistance The insulation resistance of the produced multilayer ceramic capacitor was measured with a high resistance meter (manufactured by Hewlett-Packard, model 4329A).
In addition, the measurement was performed again after being left for 500 hours under high temperature and high humidity conditions of 60 ° C. and 95% RH. In measurement voltage 50 V, those insulation resistance of more than 1 × 10 9 "○", and those less than 1 × 10 9 as "×".
（１）で作製した試料１の３級アミン置換ポリスチレンを、銅粉に対して２質量％溶解させたテトラヒドロフラン溶液に、鱗片状銅粉末（福田金属箔粉工業製、品番３Ｌ３、平均粒径１３．１μｍ）を浸積して形成した溶液を５分間撹拌した後に、銅粉をろ過により分離し、真空条件下で乾燥させて試料１の３級アミン置換ポリスチレンで被覆した鱗片状銅粉末を作製した。
その銅粉末を用いて、外部電極用銅ペースト組成物を作製、焼成して銅外部電極を形成し、実施例１に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定して、その測定結果を表２に示す。
In a tetrahydrofuran solution prepared by dissolving 2% by mass of the tertiary amine-substituted polystyrene of Sample 1 prepared in (1) with respect to copper powder, scaly copper powder (manufactured by Fukuda Metal Foil Powder Industry, product number 3L3, average particle size 13 .1 μm) was immersed in the solution formed for 5 minutes, and then the copper powder was separated by filtration and dried under vacuum conditions to produce a scaly copper powder coated with the tertiary amine-substituted polystyrene of Sample 1. did.
Using the copper powder, a copper paste composition for external electrodes was prepared and fired to form a copper external electrode, and a multilayer ceramic capacitor for characteristic evaluation according to Example 1 was prepared. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured, and the measurement results are shown in Table 2.
試料２の３級アミン置換ポリスチレンを用いた以外は、実施例１と同様の条件で実施例２に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定した。その測定結果を表２に示す。 A multilayer ceramic capacitor for characteristic evaluation according to Example 2 was produced under the same conditions as in Example 1 except that the tertiary amine-substituted polystyrene of Sample 2 was used. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured. The measurement results are shown in Table 2.
試料３の３級アミン置換ポリスチレンを用いた以外は、実施例１と同様の条件で実施例３に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定した。その測定結果を表２に示す。 A multilayer ceramic capacitor for characteristic evaluation according to Example 3 was produced under the same conditions as in Example 1 except that the tertiary amine-substituted polystyrene of Sample 3 was used. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured. The measurement results are shown in Table 2.
試料１の３級アミン置換ポリスチレンを銅粉に対して５質量％溶解させたテトラヒドロフラン溶液に、鱗片状銅粉末（福田金属箔粉工業製、品番３Ｌ３、平均粒径１３．１μｍ）を浸積し、その溶液を５分間撹拌した後に銅粉をろ過により分離し、真空条件下で乾燥させて試料１の３級アミン置換ポリスチレンで被覆された鱗片状銅粉を作製した。
その銅粉末を用いて、外部電極用銅ペースト組成物を作製、焼成して銅外部電極を形成し、実施例４に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定して、その測定結果を表２に示す。
A scaly copper powder (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., product number 3L3, average particle size 13.1 μm) is immersed in a tetrahydrofuran solution prepared by dissolving 5% by mass of the tertiary amine-substituted polystyrene of Sample 1 with respect to copper powder After the solution was stirred for 5 minutes, the copper powder was separated by filtration and dried under vacuum conditions to prepare a scaly copper powder coated with the tertiary amine-substituted polystyrene of Sample 1.
Using the copper powder, a copper paste composition for external electrodes was prepared and fired to form a copper external electrode, and a multilayer ceramic capacitor for characteristic evaluation according to Example 4 was prepared. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured, and the measurement results are shown in Table 2.
試料１の３級アミン置換ポリスチレンを銅粉に対して２質量％溶解させたテトラヒドロフラン溶液に、球状銅粉末（日本アトマイズ加工株式会社製、品番ＨＸＲ−Ｃｕ、粒径１μｍ）を浸積し、その溶液を５分間撹拌した後に銅粉をろ過により分離し、真空条件下で乾燥させて試料１の３級アミン置換ポリスチレンで被覆された球状銅粉を作製した。
その銅粉末を用いて、外部電極用銅ペースト組成物を作製、焼成して銅外部電極を形成し、実施例５に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定して、その測定結果を表２に示す。
A spherical copper powder (manufactured by Nippon Atomizing Co., Ltd., product number HXR-Cu, particle size 1 μm) is immersed in a tetrahydrofuran solution in which 2% by mass of the tertiary amine-substituted polystyrene of Sample 1 is dissolved with respect to copper powder. After stirring the solution for 5 minutes, the copper powder was separated by filtration and dried under vacuum conditions to produce a spherical copper powder coated with the tertiary amine-substituted polystyrene of Sample 1.
Using the copper powder, a copper paste composition for external electrodes was prepared and fired to form a copper external electrode, and a multilayer ceramic capacitor for characteristic evaluation according to Example 5 was prepared. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured, and the measurement results are shown in Table 2.
試料３の３級アミン置換ポリスチレンを、銅粉に対して２質量％溶解させたテトラヒドロフラン溶液に、球状銅粉末（日本アトマイズ加工株式会社製、品番ＨＸＲ−Ｃｕ、粒径１μｍ）を浸積し、その溶液を５分間撹拌した後に銅球状粉をろ過により分離し、真空条件下で乾燥させて試料３の３級アミン置換ポリスチレンで被覆された球状銅粉を作製した。
その銅粉末を用いて、外部電極用銅ペースト組成物を作製、焼成して銅外部電極を形成し、実施例６に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定して、その測定結果を表２に示す。
A spherical copper powder (manufactured by Nippon Atomizing Co., Ltd., product number HXR-Cu, particle size 1 μm) is immersed in a tetrahydrofuran solution in which the tertiary amine-substituted polystyrene of Sample 3 is dissolved in 2% by mass with respect to copper powder. After stirring the solution for 5 minutes, the copper spherical powder was separated by filtration and dried under vacuum conditions to produce Sample 3 coated spherical copper powder with the tertiary amine-substituted polystyrene.
Using the copper powder, a copper paste composition for external electrodes was prepared and fired to form a copper external electrode, and a multilayer ceramic capacitor for characteristic evaluation according to Example 6 was prepared. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured, and the measurement results are shown in Table 2.
（比較例１）
試料４の３級アミン置換ポリスチレンを用いた以外は、実施例１と同様の条件で比較例１に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定した。その測定結果を表２に示す。
(Comparative Example 1)
A multilayer ceramic capacitor for characteristic evaluation according to Comparative Example 1 was produced under the same conditions as in Example 1 except that the tertiary amine-substituted polystyrene of Sample 4 was used. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured. The measurement results are shown in Table 2.
（比較例２）
試料５の３級アミン置換ポリスチレンを用いた以外は、実施例１と同様の条件で比較例２に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定した。その測定結果を表２に示す。
(Comparative Example 2)
A multilayer ceramic capacitor for characteristic evaluation according to Comparative Example 2 was produced under the same conditions as in Example 1 except that the tertiary amine-substituted polystyrene of Sample 5 was used. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured. The measurement results are shown in Table 2.
（比較例３）
導電性低分子化合物であるＮ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１’−ビフェニル−４，４’−ジアミン（以下、ＴＰＤと称す）をテトラヒドロフランに溶解させ、実施例１と同様に、導電性低分子化合物のＴＰＤで被覆された鱗片状銅粉を作製した。
その銅粉末を用いて、外部電極用銅ペースト組成物を作製、焼成して銅外部電極を形成し、比較例３に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定して、その測定結果を表２に示す。
(Comparative Example 3)
N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine (hereinafter referred to as TPD), which is a conductive low-molecular compound, is used as tetrahydrofuran. It was made to melt | dissolve and the scaly copper powder coat | covered with TPD of a conductive low molecular weight compound was produced like Example 1. FIG.
Using the copper powder, a copper paste composition for external electrodes was prepared and fired to form a copper external electrode, and a multilayer ceramic capacitor for characteristic evaluation according to Comparative Example 3 was prepared. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured, and the measurement results are shown in Table 2.
（比較例４）
導電性低分子化合物の２，４，６−トリ（２−ピリジル）−１，３，５−トリアジン（以下、ＴＰＴＺと称す）をテトラヒドロフランに溶解させ、実施例１と同様にＴＰＴＺで被覆された鱗片状銅粉を作製した。
その銅粉末を用いて、外部電極用銅ペースト組成物を作製、焼成して銅外部電極を形成し、比較例４に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定して、その測定結果を表２に示す。
(Comparative Example 4)
A conductive low molecular weight compound 2,4,6-tri (2-pyridyl) -1,3,5-triazine (hereinafter referred to as TPTZ) was dissolved in tetrahydrofuran and coated with TPTZ in the same manner as in Example 1. A scaly copper powder was produced.
Using the copper powder, a copper paste composition for external electrodes was prepared and fired to form a copper external electrode, and a multilayer ceramic capacitor for characteristic evaluation according to Comparative Example 4 was prepared. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured, and the measurement results are shown in Table 2.
（比較例５）
非３級アミン置換ポリスチレンのポリスチレンをトルエンに溶解させ、実施例１と同様にポリスチレンで被覆された鱗片状銅粉を作製した。
その銅粉末を用いて、外部電極用銅ペースト組成物を作製、焼成して銅外部電極を形成し、比較例５に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定して、その測定結果を表２に示す。
(Comparative Example 5)
Non-tertiary amine-substituted polystyrene polystyrene was dissolved in toluene, and a scaly copper powder coated with polystyrene was prepared in the same manner as in Example 1.
Using the copper powder, a copper paste composition for external electrodes was prepared and fired to form a copper external electrode, and a multilayer ceramic capacitor for characteristic evaluation according to Comparative Example 5 was prepared. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured, and the measurement results are shown in Table 2.
（比較例６）
３級アミン置換ポリスチレンを被覆していない鱗片状銅粉末（福田金属箔粉工業製、品番３Ｌ３、平均粒径１３．１μｍ）を用いて、外部電極用銅ペースト組成物を作製、焼成して銅外部電極を形成し、比較例６に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定して、その測定結果を表２に示す。
(Comparative Example 6)
Using a scaly copper powder not coated with tertiary amine-substituted polystyrene (made by Fukuda Metal Foil Powder Industry Co., Ltd., product number 3L3, average particle size 13.1 μm), a copper paste composition for external electrodes was prepared and fired to produce copper. External electrodes were formed, and a multilayer ceramic capacitor for characteristic evaluation according to Comparative Example 6 was produced. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured, and the measurement results are shown in Table 2.
（比較例７）
（１）で作製した試料１の３級アミン置換ポリスチレンを銅粉に対して１質量％溶解させたテトラヒドロフラン溶液に、鱗片状銅粉末（福田金属箔粉工業製、品番３Ｌ３、平均粒径１３．１μｍ）を浸積し、その溶液を５分間撹拌した後に鱗片状銅粉をろ過により分離し、真空条件下で乾燥させて試料１の３級アミン置換ポリスチレンで被覆された鱗片状銅粉を作製した。
その銅粉末を用いて、外部電極用銅ペースト組成物を作製、焼成して銅外部電極を形成し、比較例７に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定して、その測定結果を表２に示す。
(Comparative Example 7)
In a tetrahydrofuran solution obtained by dissolving 1% by mass of the tertiary amine-substituted polystyrene of Sample 1 prepared in (1) with respect to copper powder, scaly copper powder (Fukuda Metal Foil Powder Industries, product number 3L3, average particle size 13. 1 μm), and the solution was stirred for 5 minutes, and then the scaly copper powder was separated by filtration and dried under vacuum conditions to produce a scaly copper powder coated with the tertiary amine-substituted polystyrene of Sample 1. did.
Using the copper powder, a copper paste composition for external electrodes was prepared and fired to form a copper external electrode, and a multilayer ceramic capacitor for characteristic evaluation according to Comparative Example 7 was prepared. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured, and the measurement results are shown in Table 2.
（比較例８）
（１）で作製した試料１の３級アミン置換ポリスチレンを、銅粉に対して７質量％溶解させたテトラヒドロフラン溶液に、鱗片状銅粉末（福田金属箔粉工業製、品番３Ｌ３、平均粒径１３．１μｍ）を浸積し、その溶液を５分間撹拌した後に銅粉をろ過により分離し、真空条件下で乾燥させて試料１の３級アミン置換ポリスチレンで被覆された鱗片状銅粉を作製した。
その銅粉末を用いて、外部電極用銅ペースト組成物を作製、焼成して銅外部電極を形成し、比較例８に係る特性評価用の積層セラミックコンデンサを作製した。その積層セラミックコンデサの静電容量および絶縁抵抗を測定して、その測定結果を表２に示す。
(Comparative Example 8)
In a tetrahydrofuran solution prepared by dissolving 7% by mass of the tertiary amine-substituted polystyrene of Sample 1 prepared in (1) with respect to copper powder, scaly copper powder (manufactured by Fukuda Metal Foil Powder Industry, product number 3L3, average particle size 13 .1 μm), and the solution was stirred for 5 minutes, and then the copper powder was separated by filtration and dried under vacuum conditions to produce a scale-like copper powder coated with the tertiary amine-substituted polystyrene of Sample 1. .
Using the copper powder, a copper paste composition for external electrodes was prepared and fired to form a copper external electrode, and a multilayer ceramic capacitor for characteristic evaluation according to Comparative Example 8 was prepared. The capacitance and insulation resistance of the multilayer ceramic capacitor were measured, and the measurement results are shown in Table 2.
試料４の３級アミン置換ポリスチレンを用いた比較例１では、その重量平均分子量が小さく、銅粉表面の被覆が十分でなかったために、被覆されなかった表面が酸化し、静電容量も、絶縁抵抗も「×」であった。また、重量平均分子量が大きすぎる試料５の３級アミン置換ポリスチレンをコーティング膜に用いた比較例２では、有機溶剤のテトラヒドロフラン、トルエンに溶解しなかった為、銅粉へ均一なコーティング膜を被覆させることができなかった。 In Comparative Example 1 using the tertiary amine-substituted polystyrene of Sample 4, the weight average molecular weight was small and the copper powder surface was not sufficiently coated, so the uncoated surface was oxidized, and the capacitance was also insulated. The resistance was also “x”. In Comparative Example 2 in which the tertiary amine-substituted polystyrene of Sample 5 whose weight average molecular weight is too large was used as the coating film, the uniform coating film was coated on the copper powder because it was not dissolved in the organic solvents tetrahydrofuran and toluene. I couldn't.
本発明の３級アミン置換ポリスチレンの代りに、導電性低分子化合物であるＮ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１’−ビフェニル−４，４’−ジアミン（ＴＰＤ）を用いた比較例３、および導電性低分子化合物である２，４，６−トリ（２−ピリジル）−１，３，５−トリアジン（ＴＰＴＺ）を用いた比較例４では、静電容量が劣り、高温高湿条件下での絶縁抵抗の劣化も見られる。また、非３級アミン置換ポリスチレンであるポリスチレンをトルエンに溶解したものを用いた比較例５では、静電容量、絶縁抵抗共に劣っていることが分かる。
さらに、銅粉を３級アミン置換ポリスチレンによって被覆しないで用いた比較例６では、測定したすべての特性において劣っていることがわかる。
Instead of the tertiary amine-substituted polystyrene of the present invention, N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4 ′, which is a conductive low-molecular compound, is used. In Comparative Example 3 using diamine (TPD) and Comparative Example 4 using 2,4,6-tri (2-pyridyl) -1,3,5-triazine (TPTZ), which is a conductive low molecular compound In addition, the capacitance is inferior, and the insulation resistance is deteriorated under high temperature and high humidity conditions. Moreover, it turns out that both the electrostatic capacity and the insulation resistance are inferior in the comparative example 5 using what melt | dissolved the polystyrene which is non-tertiary amine substituted polystyrene in toluene.
Furthermore, it turns out that it is inferior in all the measured characteristics in the comparative example 6 used without coat | covering copper powder with tertiary amine substituted polystyrene.
試料１の３級アミン置換ポリスチレンを銅粉に対して１質量％と少ない量を溶解させたテトラヒドロフラン溶液を用いたコーティング膜を被覆した比較例７では、測定したすべての特性が満足しなかったことがわかる。また、銅粉に対する３級アミン置換ポリスチレンの量が７質量％と多すぎる比較例８でも同様に測定したすべての特性において劣っていることがわかる。 In Comparative Example 7 in which the coating film using the tetrahydrofuran solution in which the tertiary amine-substituted polystyrene of Sample 1 was dissolved in a small amount of 1% by mass with respect to the copper powder was coated, all the measured characteristics were not satisfied. I understand. Moreover, it turns out that it is inferior in all the characteristics measured similarly also in the comparative example 8 with which the quantity of the tertiary amine substituted polystyrene with respect to copper powder is too much as 7 mass%.
一方、本発明の条件を満足する実施例１から実施例６では、静電容量、絶縁抵抗（初期、高温高湿条件下）共に、優れていることがわかる。
On the other hand, in Examples 1 to 6 that satisfy the conditions of the present invention, it can be seen that both the capacitance and the insulation resistance (initial, high temperature and high humidity conditions) are excellent.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010195027A JP2012052181A (en) | 2010-08-31 | 2010-08-31 | Copper powder for conductive paste for external electrode excellent in oxidation resistance, and copper paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010195027A JP2012052181A (en) | 2010-08-31 | 2010-08-31 | Copper powder for conductive paste for external electrode excellent in oxidation resistance, and copper paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2012052181A true JP2012052181A (en) | 2012-03-15 |
Family
ID=45905825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010195027A Pending JP2012052181A (en) | 2010-08-31 | 2010-08-31 | Copper powder for conductive paste for external electrode excellent in oxidation resistance, and copper paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2012052181A (en) |
-
2010
- 2010-08-31 JP JP2010195027A patent/JP2012052181A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101848879B (en) | Lead and cadmium free, low temperature fired X7R dielectric ceramic composition and method of making | |
| JP4338680B2 (en) | Glass frit for dielectric, dielectric ceramic composition, multilayer ceramic capacitor, and manufacturing method thereof | |
| TWI382966B (en) | Copper termination inks containing lead free and cadmium free glasses for capacitors | |
| CN1241870C (en) | Nonmagnetic ceramic and laminated ceramic parts | |
| JP2012174797A (en) | Conductive paste for photogravure used for multilayer ceramic capacitor internal electrode | |
| JP2012134120A (en) | Conductive paste composition for external electrode, multilayer ceramic capacitor containing the same, and manufacturing method thereof | |
| JP2013030754A (en) | Multilayer ceramic electronic component | |
| TW200418221A (en) | Terminal electrode compositions for multilayer ceramic capacitors | |
| JP3697401B2 (en) | Conductor paste and method for producing the same | |
| JP2003100144A (en) | Conductive paste, manufacturing method of laminated ceramic electronic component and laminated ceramic electronic component | |
| JP5476631B2 (en) | Electronic component and manufacturing method thereof | |
| JP4561574B2 (en) | Conductive paste for multilayer ceramic component terminal electrode | |
| US10193332B2 (en) | ESD protection device | |
| EP3419028B1 (en) | Conductive paste | |
| CN115461825A (en) | Thick film resistor paste, thick film resistor, and electronic component | |
| WO2020166361A1 (en) | Electroconductive paste, electronic component, and laminated ceramic capacitor | |
| JP6630208B2 (en) | Method for producing metal powder paste, screen printing method for metal powder paste, method for producing electrodes, method for producing chip multilayer ceramic capacitor, and metal powder paste | |
| TW200417531A (en) | Terminal electrode compositions for multilayer ceramic capacitors | |
| JP2018152218A (en) | Conductive paste, chip electronic component and method for producing the same | |
| JP2012052181A (en) | Copper powder for conductive paste for external electrode excellent in oxidation resistance, and copper paste | |
| JPH08161931A (en) | Conductive paste, and conductive body and multilayer ceramic board using it | |
| JP5998785B2 (en) | Laminated electronic components | |
| JP4893786B2 (en) | Conductive paste | |
| WO2022114121A1 (en) | Conductive paste and multilayer ceramic capacitor | |
| WO2021221175A1 (en) | Thick film resistor paste, thick film resistor, and electronic component |