JP2020167157A - Conductive composition, metallized substrate, and methods for producing the same - Google Patents
Conductive composition, metallized substrate, and methods for producing the same Download PDFInfo
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- JP2020167157A JP2020167157A JP2020053165A JP2020053165A JP2020167157A JP 2020167157 A JP2020167157 A JP 2020167157A JP 2020053165 A JP2020053165 A JP 2020053165A JP 2020053165 A JP2020053165 A JP 2020053165A JP 2020167157 A JP2020167157 A JP 2020167157A
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- metal
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- mass
- conductive composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 239000000758 substrate Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title description 34
- 239000002245 particle Substances 0.000 claims abstract description 118
- 229910052751 metal Inorganic materials 0.000 claims abstract description 76
- 239000002184 metal Substances 0.000 claims abstract description 70
- 239000011521 glass Substances 0.000 claims abstract description 47
- 239000002923 metal particle Substances 0.000 claims abstract description 34
- 239000000919 ceramic Substances 0.000 claims abstract description 29
- 229910052709 silver Inorganic materials 0.000 claims abstract description 25
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 22
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 21
- 239000011246 composite particle Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005388 borosilicate glass Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 35
- 238000010304 firing Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 79
- 239000010949 copper Substances 0.000 description 65
- 239000011572 manganese Substances 0.000 description 65
- 150000001875 compounds Chemical class 0.000 description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 43
- 238000007747 plating Methods 0.000 description 25
- -1 K and Na) Chemical class 0.000 description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 23
- 239000010408 film Substances 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 12
- 150000004671 saturated fatty acids Chemical class 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 238000005987 sulfurization reaction Methods 0.000 description 11
- 150000002736 metal compounds Chemical class 0.000 description 10
- 238000007639 printing Methods 0.000 description 10
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- 229930195729 fatty acid Natural products 0.000 description 9
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- 239000000843 powder Substances 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000005751 Copper oxide Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910000431 copper oxide Inorganic materials 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 239000000344 soap Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229940120693 copper naphthenate Drugs 0.000 description 5
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- SGLXWMAOOWXVAM-UHFFFAOYSA-L manganese(2+);octanoate Chemical compound [Mn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O SGLXWMAOOWXVAM-UHFFFAOYSA-L 0.000 description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- 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 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 210000004718 centriole Anatomy 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- CLUOTFHJTGLPSG-UHFFFAOYSA-L copper;7,7-dimethyloctanoate Chemical compound [Cu+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O CLUOTFHJTGLPSG-UHFFFAOYSA-L 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
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- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 2
- SLEMZXQMOMKPCD-UHFFFAOYSA-L 7,7-dimethyloctanoate;iron(2+) Chemical compound [Fe+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O SLEMZXQMOMKPCD-UHFFFAOYSA-L 0.000 description 2
- BDPWLKPVAKYQNL-UHFFFAOYSA-L 7,7-dimethyloctanoate;manganese(2+) Chemical compound [Mn+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O BDPWLKPVAKYQNL-UHFFFAOYSA-L 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
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- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- FRVCGRDGKAINSV-UHFFFAOYSA-L iron(2+);octadecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRVCGRDGKAINSV-UHFFFAOYSA-L 0.000 description 2
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- 229940093474 manganese carbonate Drugs 0.000 description 2
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
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- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- DOVLHZIEMGDZIW-UHFFFAOYSA-N [Cu+3].[O-]B([O-])[O-] Chemical compound [Cu+3].[O-]B([O-])[O-] DOVLHZIEMGDZIW-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、エレクトロニクス分野において、セラミックス基板上に回路を形成するために利用される導電性組成物ならびにこの組成物で形成された回路を有するメタライズド基板およびその製造方法に関する。 The present invention relates to a conductive composition used for forming a circuit on a ceramic substrate in the field of electronics, a metallized substrate having a circuit formed by the composition, and a method for producing the same.
導電性組成物（導電性ペースト）は、印刷などにより電極など、種々のパターンを容易に形成できるため、エレクトロニクス分野で広く普及している。導電性金属粉に銀を含む銀ペーストは、電子部品などの電極や回路を形成するために用いられているが、空気中の硫黄性ガスなどにより銀が硫化されて、電極が断線したり変色したりする問題があり、銀にパラジウムを添加することで硫化を防止することが知られている。 The conductive composition (conductive paste) is widely used in the electronics field because various patterns such as electrodes can be easily formed by printing or the like. Silver paste containing silver in conductive metal powder is used to form electrodes and circuits for electronic parts, etc., but silver is sulfided by sulfurous gas in the air, causing the electrodes to break or discolor. It is known that adding palladium to silver prevents sulfide.
また、電子部品は、使用環境変化に関わらず、信頼性の高いものが要求されており、耐硫化性、高密着性、耐めっき性、耐はんだ性、信頼性（過酷な環境での使用に耐え得る密着性）等の特性を全て満たす導電性ペーストが求められている。 In addition, electronic components are required to have high reliability regardless of changes in the usage environment, and are sulfur-resistant, high-adhesion, plating-resistant, solder-resistant, and reliable (for use in harsh environments). There is a demand for a conductive paste that satisfies all the characteristics such as withstand adhesion).
特開昭５９−１３２５０２号公報（特許文献１）には、粒状銀粉およびフレーク状銀粉からなる銀粉と、少量のパラジウム粉とを導電成分として含有し、かつガラス粉を含む導電被膜形成用組成物が開示されている。 Japanese Patent Application Laid-Open No. 59-132502 (Patent Document 1) describes a composition for forming a conductive film containing glass powder and silver powder composed of granular silver powder and flake-shaped silver powder as a conductive component and a small amount of palladium powder. Is disclosed.
特開昭５９−１３２５０３号公報（特許文献２）には、導電成分として、銀粉と、パラジウム粉、酸化パラジウム粉および銀パラジウム合金粉からなる群から選ばれる少なくとも一種とを含有する導電被膜形成用組成物が開示されている。 Japanese Patent Application Laid-Open No. 59-132503 (Patent Document 2) contains silver powder and at least one selected from the group consisting of palladium powder, palladium oxide powder and silver-palladium alloy powder as a conductive component for forming a conductive film. The composition is disclosed.
特開２００４−２５０３０８号公報（特許文献３）には、銀粉末、パラジウム粉末、銅粉末を導電成分として含有し、ガラス粉を含む導電ペーストが開示されている。鉛を含まないＳｉＯ２−Ｂｉ−Ｂａ系無鉛無アルカリガラスを用いて、耐酸性、耐硫化性及びはんだ濡れ性が良好な電極が得られている。実施例では、球状銀粉末、フレーク状銀粉末、銅粉末、ガラスフリット、パラジウム粉末を含む導電ペーストが調製されている。 Japanese Unexamined Patent Publication No. 2004-250308 (Patent Document 3) discloses a conductive paste containing silver powder, palladium powder, and copper powder as conductive components and containing glass powder. Using lead-free SiO 2- Bi-Ba-based lead-free alkali-free glass, electrodes having good acid resistance, sulfurization resistance, and solder wettability have been obtained. In the examples, a conductive paste containing spherical silver powder, flaky silver powder, copper powder, glass frit, and palladium powder is prepared.
しかし、特許文献１〜３では、信頼性に関する評価はされていない。 However, in Patent Documents 1 to 3, reliability is not evaluated.
特開平０７−３０２５１０号公報（特許文献４）には、電極と抵抗体を同時焼成する際にクラックの発生やガラスの滲み出しを防止できる導電ペーストとして、微細球状銀粉と、粗粒球状銀粉または球状銀被覆ニッケル及びフレーク状銀粉と、フレーク状銀粉とを導電成分とする導電ペースト組成物が開示されている。この文献には、銀の硫化を防ぐため、パラジウムを添加してもよいと記載されている。さらに、基板と電極との接着強度を高めるために、ガラスフリットや無機結合剤として銅または酸化銅を添加すればよいと記載されている。 Japanese Patent Application Laid-Open No. 07-302510 (Patent Document 4) describes fine spherical silver powder, coarse-grained spherical silver powder, or coarse-grained spherical silver powder as a conductive paste that can prevent cracks and glass bleeding when the electrode and the resistor are simultaneously fired. A conductive paste composition containing spherical silver-coated nickel and flake-shaped silver powder and flake-shaped silver powder as conductive components is disclosed. The document states that palladium may be added to prevent the sulfurization of silver. Further, it is described that copper or copper oxide may be added as a glass frit or an inorganic binder in order to increase the adhesive strength between the substrate and the electrode.
しかし、この組成物では、１５０℃２４時間でのエージング試験により物性の低下は見られないが、信頼性を評価するには十分な評価とはいえない。 However, with this composition, although no deterioration in physical properties is observed in the aging test at 150 ° C. for 24 hours, it cannot be said that the evaluation is sufficient for evaluating the reliability.
特開平０７−３３５４０２号公報（特許文献５）には、チップ抵抗器上面電極用ペーストの導電性粉末として、平均粒径０．１〜０．５μｍの球状銀粉と平均粒径０．５〜１．５μｍの球状銀被覆パラジウム粉とを組み合わせて、焼成膜の緻密性を向上させることが開示されている。この文献には、基板との高い接着強度を得るために、無機結合剤として、銅および／または酸化銅を添加することが記載されている。 Japanese Patent Application Laid-Open No. 07-335402 (Patent Document 5) describes spherical silver powder having an average particle size of 0.1 to 0.5 μm and an average particle size of 0.5 to 1 as conductive powder of the paste for the top electrode of the chip resistor. It is disclosed that the compactness of the fired film is improved in combination with a .5 μm spherical silver-coated palladium powder. This document describes the addition of copper and / or copper oxide as an inorganic binder in order to obtain high adhesive strength to the substrate.
しかし、このペーストでも、パラジウムの割合が高いため、導電性が低くなることや、コストが高くなることが懸念される。 However, even in this paste, since the proportion of palladium is high, there is a concern that the conductivity will be low and the cost will be high.
特表２０１０−５３２５８６号公報（特許文献６）には、６５０℃以下で焼成するセラミック基板用導体ペーストとして、銀粉末と、銀パラジウム共沈粉末とを組み合わせたペーストが開示されている。 Japanese Patent Application Laid-Open No. 2010-532586 (Patent Document 6) discloses a paste in which silver powder and silver-palladium co-precipitated powder are combined as a conductor paste for a ceramic substrate to be fired at 650 ° C. or lower.
しかし、このペーストは、高温での焼成に対応していない。 However, this paste is not compatible with baking at high temperatures.
従って、本発明の目的は、セラミックス基板に対して密着性が高い導電部を形成できる導電性組成物ならびにこの組成物で形成された導電部を有するメタライズド基板およびその製造方法を提供することにある。 Therefore, an object of the present invention is to provide a conductive composition capable of forming a conductive portion having high adhesion to a ceramic substrate, a metallized substrate having a conductive portion formed of this composition, and a method for producing the same. ..
本発明の他の目的は、耐硫化性が高く、使用環境の変化に拘わらず、セラミックス基板に対して密着性が高い導電部を形成できる導電性組成物ならびにこの組成物で形成された導電部を有するメタライズド基板およびその製造方法を提供することにある。 Another object of the present invention is a conductive composition having high sulfurization resistance and capable of forming a conductive portion having high adhesion to a ceramic substrate regardless of changes in the usage environment, and a conductive portion formed of this composition. To provide a metallized substrate and a method for manufacturing the same.
本発明のさらに他の目的は、信頼性の高いメタライズド基板を製造できる導電性組成物ならびにこの組成物で形成された導電部を有するメタライズド基板およびその製造方法を提供することにある。 Still another object of the present invention is to provide a conductive composition capable of producing a highly reliable metallized substrate, a metallized substrate having a conductive portion formed of the composition, and a method for producing the same.
本発明者は、前記課題を達成するため鋭意検討した結果、Ａｇ粒子（Ａ１）ならびにＡｇおよびＰｄの複合粒子（Ａ２）からなる金属粒子（Ａ）と、ガラス粒子（Ｂ）と、Ｍｎ成分（Ｃ１）、Ｆｅ成分（Ｃ２）およびＣｕ成分（Ｃ３）からなる金属成分（Ｃ）とを組み合わせ、前記金属成分（Ｃ）が有機金属化合物を含むことにより、セラミック基板に対して密着性が高い導電部を形成できることを見出し、本発明を完成した。 As a result of diligent studies to achieve the above object, the present inventor has made metal particles (A) composed of Ag particles (A1) and composite particles (A2) of Ag and Pd, glass particles (B), and an Mn component (Mn component). By combining a metal component (C) composed of C1), an Fe component (C2) and a Cu component (C3) and the metal component (C) containing an organometallic compound, conductivity having high adhesion to a ceramic substrate is achieved. The present invention was completed by finding that a portion can be formed.
すなわち、本発明の導電性組成物は、金属粒子（Ａ）、ガラス粒子（Ｂ）および金属成分（Ｃ）を含む導電性組成物であって、前記金属粒子（Ａ）が、Ａｇ粒子（Ａ１）ならびにＡｇおよびＰｄの複合粒子（Ａ２）であるとともに、前記金属成分（Ｃ）が、Ｍｎ成分（Ｃ１）、Ｆｅ成分（Ｃ２）およびＣｕ成分（Ｃ３）であり、かつ前記金属成分（Ｃ）が有機金属化合物を含む。前記金属成分（Ｃ）の割合は、金属元素換算で、金属粒子（Ａ）１００質量部に対して０．２〜３質量部程度である。前記有機金属化合物はカルボン酸金属塩であってもよい。前記ガラス粒子（Ｂ）はホウケイ酸ガラス粒子および／または亜鉛系ガラス粒子を含んでいてもよい。 That is, the conductive composition of the present invention is a conductive composition containing a metal particle (A), a glass particle (B) and a metal component (C), and the metal particle (A) is an Ag particle (A1). ) And the composite particles of Ag and Pd (A2), and the metal component (C) is the Mn component (C1), the Fe component (C2) and the Cu component (C3), and the metal component (C). Includes organic metal compounds. The ratio of the metal component (C) is about 0.2 to 3 parts by mass with respect to 100 parts by mass of the metal particles (A) in terms of metal elements. The organometallic compound may be a carboxylic acid metal salt. The glass particles (B) may contain borosilicate glass particles and / or zinc-based glass particles.
本発明には、前記有機金属化合物を液状組成物の形態で添加する前記導電性組成物の製造方法も含まれる。 The present invention also includes a method for producing the conductive composition in which the organometallic compound is added in the form of a liquid composition.
本発明には、セラミックス基板に前記導電性組成物を付着させる付着工程、および前記セラミックス基板に付着した前記導電性組成物を焼成して導電部を形成する焼成工程を含むメタライズド基板の製造方法も含まれる。前記焼成工程において、空気中で導電性組成物を焼成してもよい。 The present invention also comprises a method for producing a metallized substrate, which comprises a bonding step of adhering the conductive composition to the ceramic substrate and a firing step of firing the conductive composition adhered to the ceramic substrate to form a conductive portion. included. In the firing step, the conductive composition may be fired in air.
本発明には、前記製造方法で得られたメタライズド基板も含まれる。前記セラミックス基板は、アルミナ基板、アルミナ−ジルコニア基板、窒化アルミニウム基板、窒化ケイ素基板または炭化ケイ素基板であってもよい。 The present invention also includes a metallized substrate obtained by the above-mentioned manufacturing method. The ceramic substrate may be an alumina substrate, an alumina-zirconia substrate, an aluminum nitride substrate, a silicon nitride substrate, or a silicon carbide substrate.
なお、本明細書および特許請求の範囲において「金属成分」とは、金属単体、金属化合物を含む意味で用いる。Ｍｎ成分、Ｆｅ成分およびＣｕ成分も同様である。 In the present specification and claims, the term "metal component" is used to include a simple substance of a metal and a metal compound. The same applies to the Mn component, Fe component and Cu component.
本発明では、Ａｇ粒子（Ａ１）ならびにＡｇおよびＰｄの複合粒子（Ａ２）からなる金属粒子（Ａ）と、ガラス粒子（Ｂ）と、Ｍｎ成分（Ｃ１）、Ｆｅ成分（Ｃ２）およびＣｕ成分（Ｃ３）からなる金属成分（Ｃ）とを組み合わせ、前記金属成分（Ｃ）が有機金属化合物を含むため、セラミックス基板に対して密着性が高い導電部を形成できる。また、耐硫化性が高く、使用環境の変化に拘わらず、セラミックス基板に対して密着性が高い導電部を形成できる。そのため、耐めっき性にも優れている。さらに、優れた導電性を示し、高温高湿や急激な温度変化などの過酷な条件でもセラミックス基板に対する高い密着性を維持でき、信頼性の高いメタライズド基板を製造できる。 In the present invention, a metal particle (A) composed of an Ag particle (A1) and a composite particle (A2) of Ag and Pd, a glass particle (B), an Mn component (C1), an Fe component (C2) and a Cu component ( In combination with the metal component (C) composed of C3), the metal component (C) contains an organic metal compound, so that a conductive portion having high adhesion to the ceramic substrate can be formed. In addition, it is possible to form a conductive portion having high sulfurization resistance and high adhesion to a ceramic substrate regardless of changes in the usage environment. Therefore, it is also excellent in plating resistance. Further, it exhibits excellent conductivity, can maintain high adhesion to a ceramic substrate even under harsh conditions such as high temperature and high humidity and sudden temperature change, and can manufacture a highly reliable metallized substrate.
［金属粒子（Ａ）］
本発明の導電性組成物は、金属粒子（Ａ）を含む。この金属粒子（Ａ）は、Ａｇ粒子（Ａ１）ならびにＡｇおよびＰｄの複合粒子（Ａ２）との組み合わせである。
[Metal particles (A)]
The conductive composition of the present invention contains metal particles (A). The metal particles (A) are a combination of Ag particles (A1) and composite particles of Ag and Pd (A2).
（Ａｇ粒子（Ａ１））
Ａｇ粒子（Ａ１）の形状としては、例えば、球状（真球状または略球状）、楕円体（楕円球）状、多面体状（多角錐状、立方体状や直方体状などの多角柱状など）、ロッド状または棒状、繊維状、樹針状、不定形状などが挙げられる。これらのうち、セラミックス基板に対する密着性を向上できる点から、球状、楕円体状、多面体状、不定形状などの粒状が好ましく、球状や正多面体状（正六面体状または立方体状、正八面体状など）などの等方形状（特に、球状）が特に好ましい。
(Ag particles (A1))
The shape of the Ag particle (A1) is, for example, spherical (true spherical or substantially spherical), ellipsoidal (elliptical sphere), polyhedral (polyhedral pyramid, cubic or rectangular parallelepiped, etc.), rod-shaped. Alternatively, rod-shaped, fibrous, dendritic, irregular-shaped and the like can be mentioned. Of these, granules such as spherical, elliptical, polyhedral, and indefinite are preferable from the viewpoint of improving adhesion to the ceramic substrate, and spherical or regular polyhedron (regular hexahedron or cube, regular octahedron, etc.). An isotropic shape (particularly spherical) such as is particularly preferable.
なお、本明細書および特許請求の範囲において、「球状」は、真球状および略球状の双方を含む意味で用いる。球状において、短径に対する長径の比は、例えば１〜２、好ましくは１〜１．５、さらに好ましくは１〜１．３、より好ましくは１〜１．２、最も好ましくは１〜１．１である。 In the present specification and claims, "spherical" is used to mean both true spherical and substantially spherical. In the sphere, the ratio of the major axis to the minor axis is, for example, 1-2, preferably 1-1.5, more preferably 1-1.3, more preferably 1-1.2, most preferably 1-1.1. Is.
Ａｇ粒子（Ａ１）の粒径は、特に限定されず、中心粒径（Ｄ５０）として０．５〜３０μｍ程度の範囲から選択でき、中心粒径は、例えば０．７〜１０μｍであり、１μｍ以上が好ましく、例えば１〜１０μｍ（例えば１〜７．５μｍ）、好ましくは１〜４μｍ、さらに好ましくは１．５〜３μｍ（特に１．５〜２．５μｍ）程度である。中心粒径が小さすぎると、セラミックス基板に対する密着性が低下する虞があり、逆に大きすぎても、同様に密着性が低下する虞がある。 The particle size of the Ag particles (A1) is not particularly limited, and the center particle size (D50) can be selected from the range of about 0.5 to 30 μm, and the center particle size is, for example, 0.7 to 10 μm, which is 1 μm or more. Is preferable, for example, 1 to 10 μm (for example, 1 to 7.5 μm), preferably 1 to 4 μm, and more preferably 1.5 to 3 μm (particularly 1.5 to 2.5 μm). If the centriole particle size is too small, the adhesion to the ceramic substrate may decrease, and conversely, if it is too large, the adhesion may decrease as well.
なお、本明細書および特許請求の範囲では、粒子（後述する他の粒子も含む）の中心粒径は、レーザー回折散乱式粒度分布測定装置を用いて測定された平均粒径（体積基準）を意味する。 In the present specification and claims, the central particle size of particles (including other particles described later) is the average particle size (volume basis) measured using a laser diffraction / scattering type particle size distribution measuring device. means.
（複合粒子（Ａ２））
複合粒子（Ａ２）は、金属成分としてＡｇおよびＰｄを含んでいればよく、製法由来などの不純物を含んでいてもよいが、ＡｇおよびＰｄを主成分として含むことが好ましい。複合粒子（Ａ２）中のＡｇおよびＰｄの合計割合は５０質量％以上であってもよく、好ましくは８０質量％以上、さらに好ましくは９０質量％以上であり、ＡｇおよびＰｄのみからなる１００質量％が特に好ましい。
(Composite particle (A2))
The composite particle (A2) may contain Ag and Pd as metal components and may contain impurities derived from a production method, but it is preferable that Ag and Pd are contained as main components. The total ratio of Ag and Pd in the composite particle (A2) may be 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass consisting of only Ag and Pd. Is particularly preferable.
複合粒子（Ａ２）中のＰｄ含量は、導電性組成物中のＡｇおよびＰｄの総量に対して、Ｐｄの割合が０．１〜１０質量％程度となるように調整すればよい。Ｐｄの割合は、導電性組成物中のＡｇおよびＰｄの総量に対して、例えば０．３〜８質量％、好ましくは０．５〜５質量％、さらに好ましくは１〜４質量％、より好ましくは１．５〜３質量％、最も好ましくは１．５〜２．５質量％となるように、複合粒子（Ａ２）中のＰｄ含量を調整してもよい。Ｐｄの割合が少なすぎると、耐硫化性が低下する虞があり、逆に多すぎると、セラミックス基板に対する密着性が低下する虞がある。 The Pd content in the composite particles (A2) may be adjusted so that the ratio of Pd to the total amount of Ag and Pd in the conductive composition is about 0.1 to 10% by mass. The ratio of Pd is, for example, 0.3 to 8% by mass, preferably 0.5 to 5% by mass, and more preferably 1 to 4% by mass, based on the total amount of Ag and Pd in the conductive composition. The Pd content in the composite particle (A2) may be adjusted so as to be 1.5 to 3% by mass, most preferably 1.5 to 2.5% by mass. If the proportion of Pd is too small, the sulfurization resistance may decrease, and if it is too large, the adhesion to the ceramic substrate may decrease.
複合粒子（Ａ２）の複合形態は、特に限定されず、ＡｇおよびＰｄの合金粒子、ＡｇおよびＰｄの共沈粒子、Ａｇで被覆されたＰｄ粒子、Ｐｄで被覆されたＡｇ粒子などであってもよい。 The composite form of the composite particle (A2) is not particularly limited, and may be an alloy particle of Ag and Pd, a coprecipitated particle of Ag and Pd, a Pd particle coated with Ag, an Ag particle coated with Pd, and the like. Good.
共沈粒子としては、例えば、Ａｇ粒子とＰｄ粒子とが均一に混合して凝集した粉末、Ａｇ粒子またはＰｄ粒子が凝集してコア部を形成した二重層構造の粒子などが挙げられる。 Examples of the coprecipitated particles include powder in which Ag particles and Pd particles are uniformly mixed and aggregated, and particles having a double layer structure in which Ag particles or Pd particles are aggregated to form a core portion.
Ａｇで被覆されたＰｄ粒子としては、例えば、少なくとも表面の一部がＡｇで被覆されたＰｄ粒子またはＰｄ合金粒子などが挙げられる。Ｐｄで被覆されたＡｇ粒子としては、例えば、少なくとも表面の一部がＰｄで被覆されたＡｇ粒子またはＡｇ合金粒子などが挙げられる。前記Ｐｄ合金粒子において、合金を形成するための他の金属としては、例えば、Ｍｎ、Ｆｅ、Ｃｕ、Ａｇ、Ｐｔなどが挙げられる。前記Ａｇ合金粒子において、合金を形成するための他の金属としては、例えば、Ｍｎ、Ｆｅ、Ｃｕ、Ｐｄ、Ｐｔなどが挙げられる。 Examples of the Ag-coated Pd particles include Pd particles or Pd alloy particles whose surface is partially coated with Ag. Examples of the Ag particles coated with Pd include Ag particles or Ag alloy particles whose surface is partially coated with Pd. Examples of other metals for forming an alloy in the Pd alloy particles include Mn, Fe, Cu, Ag, and Pt. Examples of other metals for forming an alloy in the Ag alloy particles include Mn, Fe, Cu, Pd, and Pt.
複合粒子（Ａ２）の形状は、好ましい態様も含め、前記Ａｇ粒子（Ａ１）と同一である。 The shape of the composite particle (A2) is the same as that of the Ag particle (A1), including the preferred embodiment.
複合粒子（Ａ２）の粒径は、特に限定されず、中心粒径（Ｄ５０）として０．１〜３０μｍ程度の範囲から選択でき、中心粒径は、例えば０．２〜１０μｍ、好ましくは０．３〜５μｍ、さらに好ましくは０．５〜３μｍ（特に０．８〜２μｍ）程度である。中心粒径が小さすぎると、セラミックス基板に対する密着性が低下する虞があり、逆に大きすぎても、同様に密着性が低下する虞がある。 The particle size of the composite particles (A2) is not particularly limited, and the center particle size (D50) can be selected from the range of about 0.1 to 30 μm, and the center particle size is, for example, 0.2 to 10 μm, preferably 0. It is about 3 to 5 μm, more preferably 0.5 to 3 μm (particularly 0.8 to 2 μm). If the centriole particle size is too small, the adhesion to the ceramic substrate may decrease, and conversely, if it is too large, the adhesion may decrease as well.
複合粒子（Ａ２）の割合は、Ａｇ粒子（Ａ１）１００質量部に対して、例えば１０〜１５０質量部、好ましくは２０〜１００質量部、さらに好ましくは４０〜８０質量部、より好ましくは５０〜７０質量部、最も好ましくは６０〜７０質量部程度である。複合粒子（Ａ２）の割合が少なすぎると、耐硫化性が低下する虞があり、逆に多すぎると、セラミックス基板に対する密着性が低下する虞がある。 The ratio of the composite particles (A2) is, for example, 10 to 150 parts by mass, preferably 20 to 100 parts by mass, more preferably 40 to 80 parts by mass, and more preferably 50 to 50 parts by mass with respect to 100 parts by mass of the Ag particles (A1). It is about 70 parts by mass, most preferably about 60 to 70 parts by mass. If the proportion of the composite particles (A2) is too small, the sulfurization resistance may decrease, and conversely, if the proportion of the composite particles (A2) is too large, the adhesion to the ceramic substrate may decrease.
（金属粒子（Ａ）の割合）
金属粒子（Ａ）の割合は、導電性組成物中１０〜９９質量％程度の範囲から選択でき、例えば３０〜９８質量％、好ましくは５０〜９５質量％（例えば５０〜９２質量％）、さらに好ましくは８０〜９０質量％（特に８５〜８８質量％）程度である。金属粒子（Ａ）の割合が少なすぎると、導電性や耐硫化性が低下する虞があり、逆に多すぎると、セラミックス基板に対する密着性が低下する虞がある。
(Ratio of metal particles (A))
The proportion of the metal particles (A) can be selected from the range of about 10 to 99% by mass in the conductive composition, for example, 30 to 98% by mass, preferably 50 to 95% by mass (for example, 50 to 92% by mass), and further. It is preferably about 80 to 90% by mass (particularly 85 to 88% by mass). If the proportion of the metal particles (A) is too small, the conductivity and sulfurization resistance may decrease, and if the proportion is too large, the adhesion to the ceramic substrate may decrease.
［ガラス粒子（Ｂ）］
ガラス粒子（ガラス粉末）（Ｂ）は、焼結助剤として機能すればよく、導電体に利用される慣用のガラス粒子を利用できる。
[Glass particles (B)]
The glass particles (glass powder) (B) may function as a sintering aid, and conventional glass particles used for a conductor can be used.
ガラス粒子（Ｂ）を構成するガラスの組成は、特に限定されないが、例えば、組成式ＳｉＯ２−Ｂ２Ｏ３−ＭＯ−Ｒ２Ｏ（式中、Ｍは、Ｓｉ、Ｂ以外の元素を示し、Ｒは、Ｋ、Ｎａなどのアルカリ金属を示す）で表されるホウケイ酸ガラス（シリカ系ガラス）、組成式Ａｌ２Ｏ３−ＳｉＯ２−ＭＯ−Ｒ２Ｏ（式中、Ｍは、Ａｌ、Ｓｉ以外の元素を示し、Ｒは前記に同じ）で表されるアルミノケイ酸ガラス、組成式Ａｌ２Ｏ３−ＳｉＯ２−Ｂ２Ｏ３−ＭＯ−Ｒ２Ｏ（式中、Ｍは、Ａｌ、Ｓｉ、Ｂ以外の元素を示し、Ｒは前記に同じ）で表されるアルミノホウケイ酸ガラス、組成式Ｂｉ２Ｏ３−Ｂ２Ｏ３−ＭＯ（式中、Ｍは、Ｂｉ、Ｂ以外の元素を示す）で表されるビスマス系ガラス、ＺｎＯ−ＳｉＯ２−ＭＯで表される亜鉛系ガラス（式中、Ｍは、Ｚｎ、Ｓｉ以外の元素を示す）などが挙げられる。これらのガラスは、単独でまたは二種以上組み合わせて使用できる。これらのうち、耐めっき性を向上できる点から、ホウケイ酸ガラス、亜鉛系ガラスが好ましく、ホウケイ酸ガラスが特に好ましい。これらのガラス組成を有するガラス粒子も、単独でまたは二種以上組み合わせて使用できる。 The composition of the glass constituting the glass particles (B) is not particularly limited, but for example, the composition formula SiO 2- B 2 O 3- MO-R 2 O (in the formula, M represents an element other than Si and B). , R indicates an alkali metal such as K and Na), borosilicate glass (silica-based glass), composition formula Al 2 O 3 -SiO 2- MO-R 2 O (in the formula, M is Al). Aluminosilicate glass represented by (R is the same as above), composition formula Al 2 O 3 −SiO 2 −B 2 O 3 −MO-R 2 O (in the formula, M is Al). , Si, indicates an element other than B, R is the same as above), aluminoborosilicate glass, composition formula Bi 2 O 3- B 2 O 3- MO (in the formula, M is other than Bi, B) Examples thereof include bismuth-based glass represented by (indicating an element) and zinc-based glass represented by ZnO-SiO 2- MO (where M represents an element other than Zn and Si). These glasses can be used alone or in combination of two or more. Of these, borosilicate glass and zinc-based glass are preferable, and borosilicate glass is particularly preferable, from the viewpoint of improving plating resistance. Glass particles having these glass compositions can also be used alone or in combination of two or more.
ガラス粒子（Ｂ）の軟化点（または融点）は、導電性組成物の焼成温度よりも低い温度であるのが好ましい。ガラス粒子の軟化点は、例えば４００〜８００℃、好ましくは４２０〜８００℃、さらに好ましくは４５０〜８００℃、より好ましくは５００〜８００℃、最も好ましくは５５０〜７９０℃程度である。軟化点が低すぎると、焼成体の強度が低下する虞があり、逆に高すぎると、溶融流動性が低下するため、バインダーとしての機能が低下する虞がある。 The softening point (or melting point) of the glass particles (B) is preferably a temperature lower than the firing temperature of the conductive composition. The softening point of the glass particles is, for example, 400 to 800 ° C., preferably 420 to 800 ° C., more preferably 450 to 800 ° C., more preferably 500 to 800 ° C., and most preferably about 550 to 790 ° C. If the softening point is too low, the strength of the fired body may decrease, and if it is too high, the melt fluidity may decrease, so that the function as a binder may decrease.
ガラス粒子（Ｂ）の形状は、好ましい態様も含めて、前記金属粒子（Ａ）と同一である。 The shape of the glass particles (B) is the same as that of the metal particles (A), including a preferred embodiment.
ガラス粒子（Ｂ）の中心粒径（Ｄ５０）は、例えば０．１〜２０μｍ、好ましくは０．５〜１０μｍ、さらに好ましくは１〜５μｍ程度である。粒径が小さすぎると、経済性が低下するとともに、組成物中での分散性も低下する虞がある。逆に粒径が大きすぎると、印刷性や焼成膜の均一性が低下するとともに、メッシュスクリーンで印刷する場合には、メッシュ目詰まりの原因となる虞もある。 The central particle size (D50) of the glass particles (B) is, for example, 0.1 to 20 μm, preferably 0.5 to 10 μm, and more preferably about 1 to 5 μm. If the particle size is too small, the economy may be lowered and the dispersibility in the composition may be lowered. On the contrary, if the particle size is too large, the printability and the uniformity of the fired film are deteriorated, and when printing with a mesh screen, it may cause mesh clogging.
ガラス粒子（Ｂ）の割合は、金属粒子（Ａ）１００質量部に対して０．０５〜１０質量部程度の範囲から選択でき、例えば０．１〜５質量部、好ましくは０．３〜３質量部、さらに好ましくは０．４〜２質量部（特に０．５〜１．５質量部）程度である。ガラス粒子（Ｂ）の割合が少なすぎると、焼結助剤としての機能が低下し、耐めっき性を向上させる効果も低下する虞があり、逆に多すぎると、導電性が低下する虞がある。 The ratio of the glass particles (B) can be selected from the range of about 0.05 to 10 parts by mass with respect to 100 parts by mass of the metal particles (A), for example, 0.1 to 5 parts by mass, preferably 0.3 to 3 parts. It is about 0.4 to 2 parts by mass (particularly 0.5 to 1.5 parts by mass) by mass. If the proportion of the glass particles (B) is too small, the function as a sintering aid may be lowered and the effect of improving the plating resistance may be lowered, and conversely, if the proportion is too large, the conductivity may be lowered. is there.
［金属成分（Ｃ）］
金属成分（Ｃ）は、Ｍｎ成分（Ｃ１）とＦｅ成分（Ｃ２）とＣｕ成分（Ｃ３）との組み合わせからなる。本発明では、導電性組成物がこの金属成分（Ｃ）を含むことにより、焼成体の緻密性を向上でき、焼成体である導電部の信頼性を向上できる。組成物調製時の粘度調整が容易であり、かつ耐めっき性を向上できる点から、有機金属化合物を含んでおり、Ｍｎ成分（Ｃ１）、Ｆｅ成分（Ｃ２）およびＣｕ成分（Ｃ３）のうち、少なくとも１種が有機金属化合物（特に、カルボン酸金属塩）であるのが好ましい。
[Metal component (C)]
The metal component (C) is composed of a combination of the Mn component (C1), the Fe component (C2), and the Cu component (C3). In the present invention, when the conductive composition contains this metal component (C), the denseness of the fired body can be improved, and the reliability of the conductive portion of the fired body can be improved. Among the Mn component (C1), Fe component (C2) and Cu component (C3), it contains an organometallic compound because it is easy to adjust the viscosity at the time of preparing the composition and the plating resistance can be improved. It is preferable that at least one is an organometallic compound (particularly, a carboxylic acid metal salt).
（Ｍｎ成分（Ｃ１））
Ｍｎ成分（Ｃ１）には、Ｍｎ単体、無機Ｍｎ化合物、有機Ｍｎ化合物が含まれる。
(Mn component (C1))
The Mn component (C1) includes a simple substance of Mn, an inorganic Mn compound, and an organic Mn compound.
無機Ｍｎ化合物としては、例えば、二酸化マンガンなどのＭｎ酸化物；ホウ化マンガン；炭酸マンガン、リン酸マンガン、ホウ酸マンガン、硫酸マンガン、硝酸マンガンなどの無機酸Ｍｎ塩；塩化マンガンなどのＭｎハロゲン化物などが挙げられる。これらの無機Ｍｎ化合物は、単独でまたは二種以上組み合わせて使用できる。これらのうち、二酸化マンガン、炭酸マンガン、リン酸マンガンが好ましい。 Examples of the inorganic Mn compound include Mn oxides such as manganese dioxide; manganese boride; manganese carbonate, manganese phosphate, manganese borate, manganese sulfate, manganese nitrate and other inorganic acid Mn salts; and manganese chloride and other Mn halides. And so on. These inorganic Mn compounds can be used alone or in combination of two or more. Of these, manganese dioxide, manganese carbonate, and manganese phosphate are preferable.
Ｍｎ単体および無機Ｍｎ化合物の形状は、好ましい態様も含めて、前記金属粒子（Ａ）と同一である。 The shapes of Mn alone and the inorganic Mn compound are the same as those of the metal particles (A), including preferred embodiments.
Ｍｎ単体および無機Ｍｎ化合物で形成された粒子の中心粒径（Ｄ５０）は、例えば０．１〜３０μｍ、好ましくは１〜２０μｍ、さらに好ましくは３〜１５μｍ程度である。粒径が小さすぎると、経済性が低下するとともに、導電性組成物中での分散性も低下する虞がある。逆に粒径が大きすぎると、印刷性や焼成膜の均一性が低下するとともに、メッシュスクリーンで印刷する場合には、メッシュ目詰まりの原因となる虞もある。 The central particle size (D50) of the particles formed of Mn alone and the inorganic Mn compound is, for example, 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably about 3 to 15 μm. If the particle size is too small, the economy may be lowered and the dispersibility in the conductive composition may be lowered. On the contrary, if the particle size is too large, the printability and the uniformity of the fired film are deteriorated, and when printing with a mesh screen, it may cause mesh clogging.
有機Ｍｎ化合物は、ギ酸マンガン、酢酸マンガン、シュウ酸マンガン、酪酸マンガン、カプロン酸マンガン、オクチル酸マンガン、ネオデカン酸マンガン、ステアリン酸マンガン、ナフテン酸マンガンなどのカルボン酸Ｍｎ塩などが挙げられる。有機Ｍｎ化合物は、Ｍｎ系金属石鹸（例えば、オクチル酸マンガン、ネオデカン酸マンガン、ステアリン酸マンガンなどの高級脂肪酸Ｍｎ塩など）であってもよい。これらの有機Ｍｎ系化合物は、単独でまたは二種以上組み合わせて使用できる。これらのうち、オクチル酸マンガンなどのＣ４−２４飽和脂肪酸Ｍｎが好ましくＣ６−１２飽和脂肪酸Ｍｎ塩が特に好ましい。有機Ｍｎ化合物（特に、Ｃ４−２４飽和脂肪酸Ｍｎ塩）は、液状組成物の形態で使用してもよい。液状組成物は、石油系炭化水素溶液などの炭化水素溶液（例えば、ミネラルスピリット溶液）であってもよい。 Examples of the organic Mn compound include manganese formate, manganese acetate, manganese oxalate, manganese butyrate, manganese caproate, manganese octylate, manganese neodecanoate, manganese stearate, manganese naphthenate and other carboxylic acid Mn salts. The organic Mn compound may be a Mn-based metal soap (for example, a higher fatty acid Mn salt such as manganese octylate, manganese neodecanoate, or manganese stearate). These organic Mn-based compounds can be used alone or in combination of two or more. Of these, C 4-24 saturated fatty acid Mn such as manganese octylate is preferable, and C 6-12 saturated fatty acid Mn salt is particularly preferable. Organic Mn compounds (particularly C 4-24 saturated fatty acid Mn salts) may be used in the form of liquid compositions. The liquid composition may be a hydrocarbon solution such as a petroleum-based hydrocarbon solution (for example, a mineral spirit solution).
Ｍｎ成分（Ｃ１）の割合は、Ｍｎ元素換算で（Ｍｎ元素の割合として）、金属粒子（Ａ）１００質量部に対して、例えば０．０１〜１質量部、好ましくは０．０３〜０．５質量部、さらに好ましくは０．０５〜０．３質量部（特に０．１〜０．２質量部）程度である。Ｍｎ成分（Ｃ１）の割合が少なすぎると、焼成体の緻密性が低下する虞があり、逆に多すぎると、導電性が低下する虞がある。 The ratio of the Mn component (C1) is, for example, 0.01 to 1 part by mass, preferably 0.03 to 0. With respect to 100 parts by mass of the metal particles (A) in terms of Mn element (as a ratio of Mn element). It is about 5 parts by mass, more preferably about 0.05 to 0.3 parts by mass (particularly 0.1 to 0.2 parts by mass). If the proportion of the Mn component (C1) is too small, the compactness of the fired body may decrease, and conversely, if it is too large, the conductivity may decrease.
（Ｆｅ成分（Ｃ２））
Ｆｅ成分（Ｃ２）には、Ｆｅ単体、無機Ｆｅ化合物、有機Ｆｅ化合物が含まれる。
(Fe component (C2))
The Fe component (C2) includes a simple substance of Fe, an inorganic Fe compound, and an organic Fe compound.
無機Ｆｅ化合物としては、例えば、酸化鉄（II）、酸化鉄（III）、四酸化三鉄などのＦｅ酸化物；ホウ化鉄；水酸化鉄；硫化鉄；炭酸鉄、リン酸鉄、ホウ酸鉄、硫酸鉄、硝酸鉄などの無機酸Ｆｅ塩；塩化鉄などのＦｅハロゲン化物などが挙げられる。これらの無機Ｆｅ化合物は、単独でまたは二種以上組み合わせて使用できる。これらのうち、酸化鉄（II）、酸化鉄（III）、四酸化三鉄、リン酸鉄が好ましい。 Examples of the inorganic Fe compound include Fe oxides such as iron (II) oxide, iron (III) oxide, and triiron tetroxide; iron borate; iron hydroxide; iron sulfide; iron carbonate, iron phosphate, boric acid. Examples thereof include inorganic acid Fe salts such as iron, iron sulfate and iron nitrate; and Fe halides such as iron chloride. These inorganic Fe compounds can be used alone or in combination of two or more. Of these, iron (II) oxide, iron (III) oxide, triiron tetroxide, and iron phosphate are preferable.
Ｆｅ単体および無機Ｆｅ化合物の形状は、好ましい態様も含めて、前記金属粒子（Ａ）と同一である。 The shapes of Fe alone and the inorganic Fe compound are the same as those of the metal particles (A), including preferred embodiments.
Ｆｅ単体および無機Ｆｅ化合物の中心粒径（Ｄ５０）は、例えば０．１〜１０μｍ、好ましくは０．５〜５μｍ、さらに好ましくは１〜３μｍ程度である。粒径が小さすぎると、経済性が低下するとともに、導電性組成物中での分散性も低下する虞がある。逆に粒径が大きすぎると、印刷性や焼成膜の均一性が低下するとともに、メッシュスクリーンで印刷する場合には、メッシュ目詰まりの原因となる虞もある。 The central particle size (D50) of the Fe simple substance and the inorganic Fe compound is, for example, 0.1 to 10 μm, preferably 0.5 to 5 μm, and more preferably about 1 to 3 μm. If the particle size is too small, the economy may be lowered and the dispersibility in the conductive composition may be lowered. On the contrary, if the particle size is too large, the printability and the uniformity of the fired film are deteriorated, and when printing with a mesh screen, it may cause mesh clogging.
有機Ｆｅ化合物としては、例えば、ギ酸鉄、酢酸鉄、シュウ酸鉄、酪酸鉄、カプロン酸鉄、オクチル酸鉄、ネオデカン酸鉄、ステアリン酸鉄、ナフテン酸鉄などのカルボン酸Ｆｅ塩；アセチルアセトン金属錯体（ナーセム第二鉄）などの金属錯体などが挙げられる。有機Ｆｅ化合物は、Ｆｅ系金属石鹸（例えば、オクチル酸鉄、ネオデカン酸鉄、ステアリン酸鉄などの高級脂肪酸Ｆｅ塩など）であってもよい。これらの有機Ｆｅ化合物は、単独でまたは二種以上組み合わせて使用できる。これらのうち、オクチル酸鉄などのＣ４−２４飽和脂肪酸Ｆｅ塩が好ましくＣ６−１２飽和脂肪酸Ｆｅ塩が特に好ましい。有機Ｆｅ化合物（特に、Ｃ４−２４飽和脂肪酸Ｆｅ塩）は、液状組成物の形態で使用してもよい。液状組成物は、石油系炭化水素溶液などの炭化水素溶液（例えば、ミネラルスピリット溶液）であってもよい。 Examples of the organic Fe compound include carboxylic acid Fe salts such as iron formate, iron acetate, iron oxalate, iron butyrate, iron caproate, iron octylate, iron neodecanoate, iron stearate, and iron naphthenate; acetylacetone metal complex. Examples include metal complexes such as (Narsem ferrous iron). The organic Fe compound may be an Fe-based metal soap (for example, a higher fatty acid Fe salt such as iron octylate, iron neodecanoate, or iron stearate). These organic Fe compounds can be used alone or in combination of two or more. Of these, C 4-24 saturated fatty acid Fe salt such as iron octylate is preferable, and C 6-12 saturated fatty acid Fe salt is particularly preferable. Organic Fe compounds (particularly C 4-24 saturated fatty acid Fe salts) may be used in the form of liquid compositions. The liquid composition may be a hydrocarbon solution such as a petroleum-based hydrocarbon solution (for example, a mineral spirit solution).
Ｆｅ成分（Ｃ２）の割合は、Ｆｅ元素換算で（Ｆｅ元素の割合として）、金属粒子（Ａ）１００質量部に対して、例えば０．０１〜１質量部、好ましくは０．０３〜０．５質量部、さらに好ましくは０．０５〜０．３質量部（特に０．１〜０．２質量部）程度である。Ｆｅ成分（Ｃ２）の割合が少なすぎると、焼成体の緻密性が低下する虞があり、逆に多すぎると、導電性が低下する虞がある。 The ratio of the Fe component (C2) is, for example, 0.01 to 1 part by mass, preferably 0.03 to 0. With respect to 100 parts by mass of the metal particles (A) in terms of Fe elements (as a ratio of Fe elements). It is about 5 parts by mass, more preferably about 0.05 to 0.3 parts by mass (particularly 0.1 to 0.2 parts by mass). If the proportion of the Fe component (C2) is too small, the compactness of the fired body may decrease, and if it is too large, the conductivity may decrease.
（Ｃｕ成分（Ｃ３））
Ｃｕ成分（Ｃ３）には、Ｃｕ単体、無機Ｃｕ化合物、有機Ｃｕ化合物が含まれる。
(Cu component (C3))
The Cu component (C3) includes a simple substance of Cu, an inorganic Cu compound, and an organic Cu compound.
無機Ｃｕ化合物としては、例えば、酸化銅などのＣｕ酸化物；水酸化銅；硫化銅；炭酸銅、リン酸銅、ホウ酸銅、硫酸銅、硝酸銅などの無機酸Ｃｕ塩；塩化銅などのＣｕハロゲン化物などが挙げられる。これらの無機Ｃｕ化合物は、単独でまたは二種以上組み合わせて使用できる。これらのうち、酸化銅、炭酸銅、リン酸銅が好ましい。 Examples of the inorganic Cu compound include Cu oxides such as copper oxide; copper hydroxide; copper sulfide; copper carbonate, copper phosphate, copper borate, copper sulfate, copper nitrate and other inorganic acid Cu salts; copper chloride and the like. Examples include Cu halides. These inorganic Cu compounds can be used alone or in combination of two or more. Of these, copper oxide, copper carbonate, and copper phosphate are preferable.
Ｃｕ単体および無機Ｃｕ化合物の形状は、好ましい態様も含めて、前記金属粒子（Ａ）と同一である。 The shapes of the Cu simple substance and the inorganic Cu compound are the same as those of the metal particles (A), including preferred embodiments.
Ｃｕ単体および無機Ｃｕ化合物の中心粒径（Ｄ５０）は、例えば０．１〜１０μｍ、好ましくは０．５〜５μｍ、さらに好ましくは１〜３μｍ程度である。粒径が小さすぎると、経済性が低下するとともに、導電性組成物中での分散性も低下する虞がある。逆に粒径が大きすぎると、印刷性や焼成膜の均一性が低下するとともに、メッシュスクリーンで印刷する場合には、メッシュ目詰まりの原因となる虞もある。 The central particle size (D50) of the Cu simple substance and the inorganic Cu compound is, for example, 0.1 to 10 μm, preferably 0.5 to 5 μm, and more preferably about 1 to 3 μm. If the particle size is too small, the economy may be lowered and the dispersibility in the conductive composition may be lowered. On the contrary, if the particle size is too large, the printability and the uniformity of the fired film are deteriorated, and when printing with a mesh screen, it may cause mesh clogging.
有機Ｃｕ化合物としては、例えば、ギ酸銅、酢酸銅、シュウ酸銅、酪酸銅、カプロン酸銅、オクチル酸銅、ネオデカン酸銅、ナフテン酸銅などのカルボン酸Ｃｕ塩、アセチルアセトン金属錯体（ナーセム銅）などの金属錯体などが挙げられる。有機Ｃｕ化合物は、Ｃｕ系金属石鹸（例えば、ネオデカン酸銅、ナフテン酸銅などの高級脂肪酸Ｃｕ塩など）であってもよい。これらの有機Ｃｕ化合物は、単独でまたは二種以上組み合わせて使用できる。これらのうち、ナフテン酸銅などの環式脂肪酸Ｃｕ塩（例えば、シクロペンタン、シクロヘキサンなどのＣ４−８シクロアルカン環を有する脂肪酸Ｃｕ塩）、ネオデカン酸銅などのＣ４−２４飽和脂肪酸Ｃｕ塩が好ましい。 Examples of the organic Cu compound include carboxylic acid Cu salts such as copper formate, copper acetate, copper oxalate, copper butyrate, copper caproate, copper octylate, copper neodecanoate, and copper naphthenate, and acetylacetone metal complexes (Nacem copper). Such as metal complexes and the like. The organic Cu compound may be a Cu-based metal soap (for example, a higher fatty acid Cu salt such as copper neodecanoate or copper naphthenate). These organic Cu compounds can be used alone or in combination of two or more. Of these, cyclic fatty acid Cu salts such as copper naphthenate (for example, fatty acid Cu salts having a C 4-8 cycloalkane ring such as cyclopentane and cyclohexane), and C 4-24 saturated fatty acid Cu salts such as copper neodecanoate. Is preferable.
Ｃｕ成分（Ｃ３）の割合は、Ｃｕ元素換算で（Ｃｕ元素の割合として）、金属粒子（Ａ）１００質量部に対して、例えば０．０１〜１質量部、好ましくは０．０３〜０．５質量部、さらに好ましくは０．０５〜０．４質量部（特に０．２〜０．３質量部）程度である。Ｃｕ化合物（Ｃ３）の割合が少なすぎると、焼成体の緻密性が低下する虞があり、逆に多すぎると、導電性が低下する虞がある。 The ratio of the Cu component (C3) is, for example, 0.01 to 1 part by mass, preferably 0.03 to 0. With respect to 100 parts by mass of the metal particles (A) in terms of Cu element (as a ratio of Cu element). It is about 5 parts by mass, more preferably about 0.05 to 0.4 parts by mass (particularly 0.2 to 0.3 parts by mass). If the proportion of the Cu compound (C3) is too small, the compactness of the fired body may decrease, and if it is too large, the conductivity may decrease.
（金属成分（Ｃ）の好ましい態様）
金属成分（Ｃ）は、耐めっき性を向上できる点から、有機金属化合物（すなわち、有機Ｍｎ化合物、有機Ｆｅ化合物または有機Ｃｕ化合物）を含んでおり、Ｍｎ成分（Ｃ１）、Ｆｅ成分（Ｃ２）およびＣｕ成分（Ｃ３）のいずれの成分が有機金属化合物を含んでいてもよい。なかでも、Ｍｎ成分（Ｃ１）、Ｆｅ成分（Ｃ２）およびＣｕ成分（Ｃ３）のうち、少なくとも１種が有機金属化合物（特に、カルボン酸金属塩）であるのが好ましく、１種または２種が有機金属化合物であるのがさらに好ましく、１種のみが有機金属化合物であるのが特に好ましい。さらに、少なくともＭｎ成分（Ｃ１）またはＦｅ成分（Ｃ２）が有機金属化合物であるのが好ましく、少なくともＭｎ成分（Ｃ１）が有機金属化合物であるのがさらに好ましく、Ｍｎ成分（Ｃ１）のみが有機金属化合物であるのが特に好ましい。特に、本発明では、前記有機金属化合物を液状組成物の形態で配合すると、耐めっき性をより向上できる。
(Preferable embodiment of the metal component (C))
The metal component (C) contains an organometallic compound (that is, an organic Mn compound, an organic Fe compound, or an organic Cu compound) from the viewpoint of improving plating resistance, and the Mn component (C1) and Fe component (C2). And any component of the Cu component (C3) may contain an organometallic compound. Among them, at least one of the Mn component (C1), Fe component (C2) and Cu component (C3) is preferably an organometallic compound (particularly, a carboxylic acid metal salt), and one or two of them are preferable. It is more preferably an organometallic compound, and it is particularly preferable that only one of them is an organometallic compound. Further, at least the Mn component (C1) or Fe component (C2) is preferably an organometallic compound, further preferably at least the Mn component (C1) is an organometallic compound, and only the Mn component (C1) is an organometallic. It is particularly preferably a compound. In particular, in the present invention, the plating resistance can be further improved by blending the organometallic compound in the form of a liquid composition.
Ｍｎ成分（Ｃ１）が有機金属化合物（特に、Ｃ６−１２飽和脂肪酸Ｍｎ塩）である場合、Ｆｅ成分（Ｃ２）は、無機Ｆｅ化合物、有機Ｆｅ化合物が好ましく、酸化鉄、カルボン酸Ｆｅ塩がさらに好ましく、Ｆｅ２Ｏ３が特に好ましい。また、Ｃｕ成分（Ｃ３）は、Ｃｕ単体、無機Ｃｕ化合物、Ｃ４−８シクロアルカン環を有する脂肪酸Ｃｕ塩が好ましく、酸化銅が特に好ましい。 When the Mn component (C1) is an organic metal compound (particularly, C 6-12 saturated fatty acid Mn salt), the Fe component (C2) is preferably an inorganic Fe compound or an organic Fe compound, and iron oxide or a carboxylic acid Fe salt. Further preferred, Fe 2 O 3 is particularly preferred. Further, as the Cu component (C3), Cu alone, an inorganic Cu compound, and a fatty acid Cu salt having a C 4-8 cycloalkane ring are preferable, and copper oxide is particularly preferable.
Ｆｅ成分（Ｃ２）が有機金属化合物（特に、Ｃ６−１２飽和脂肪酸Ｆｅ塩）である場合、Ｍｎ成分（Ｃ１）は、無機Ｍｎ化合物、有機Ｍｎ化合物が好ましく、酸化マンガン、カルボン酸Ｍｎ塩がさらに好ましい。また、Ｃｕ成分（Ｃ３）は、Ｃｕ単体、無機Ｃｕ化合物、環式脂肪酸Ｃｕ塩が好ましく、酸化銅、Ｃ４−８シクロアルカン環を有する脂肪酸Ｃｕ塩が特に好ましい。 When the Fe component (C2) is an organic metal compound (particularly, C 6-12 saturated fatty acid Fe salt), the Mn component (C1) is preferably an inorganic Mn compound or an organic Mn compound, and manganese oxide or a carboxylic acid Mn salt is preferable. More preferred. Further, as the Cu component (C3), Cu alone, an inorganic Cu compound, and a cyclic fatty acid Cu salt are preferable, and copper oxide and a fatty acid Cu salt having a C 4-8 cycloalkane ring are particularly preferable.
Ｃｕ成分（Ｃ３）が有機金属化合物（特に、Ｃ４−８シクロアルカン環を有する脂肪酸Ｃｕ塩）である場合、Ｍｎ成分（Ｃ１）は、無機Ｍｎ化合物、有機Ｍｎ化合物が好ましく、酸化マンガン、カルボン酸Ｍｎ塩がさらに好ましく、Ｃ６−１２飽和脂肪酸Ｍｎ塩が特に好ましい。また、Ｆｅ成分（Ｃ２）は、無機Ｆｅ化合物、有機Ｆｅ化合物が好ましく、酸化鉄、カルボン酸Ｆｅ塩がさらに好ましく、Ｆｅ２Ｏ３、Ｃ６−１２飽和脂肪酸Ｆｅ塩が特に好ましい。 When the Cu component (C3) is an organometallic compound (particularly, a fatty acid Cu salt having a C 4-8 cycloalkane ring), the Mn component (C1) is preferably an inorganic Mn compound or an organic Mn compound, preferably manganese oxide or a carboxylic acid. The acid Mn salt is more preferable, and the C 6-12 saturated fatty acid Mn salt is particularly preferable. The Fe component (C2) is preferably an inorganic Fe compound or an organic Fe compound, more preferably iron oxide or a carboxylic acid Fe salt, and particularly preferably Fe 2 O 3 or C 6-12 saturated fatty acid Fe salt.
これらの組み合わせのうち、Ｍｎ成分（Ｃ１）が有機金属化合物（特に、Ｃ６−１２飽和脂肪酸Ｍｎ塩）であり、Ｆｅ成分（Ｃ２）が無機Ｆｅ化合物（特に、酸化鉄）であり、Ｃｕ成分（Ｃ３）が無機Ｃｕ化合物（特に、酸化銅）である組み合わせが最も好ましい。 Among these combinations, the Mn component (C1) is an organic metal compound (particularly, C 6-12 saturated fatty acid Mn salt), the Fe component (C2) is an inorganic Fe compound (particularly iron oxide), and the Cu component. The combination in which (C3) is an inorganic Cu compound (particularly copper oxide) is most preferable.
（金属成分（Ｃ）の割合）
金属成分（Ｃ）の割合は、金属元素換算で（Ｍｎ元素、Ｆｅ元素およびＣｕ元素の合計割合として）、金属粒子（Ａ）１００質量部に対して０．１〜３．２質量部程度の範囲から選択でき、例えば０．２〜３質量部（例えば０．２５〜２質量部）、好ましくは０．３〜１．５質量部（例えば０．３５〜１．４質量部）、さらに好ましくは０．３５〜１質量部、より好ましくは０．３５〜０．８質量部、最も好ましくは０．４〜０．６質量部程度である。金属成分（Ｃ）の割合が少なすぎると、焼成体の緻密性が低下する虞があり、逆に多すぎると、導電性が低下する虞がある。
(Ratio of metal component (C))
The ratio of the metal component (C) is about 0.1 to 3.2 parts by mass with respect to 100 parts by mass of the metal particles (A) in terms of metal elements (as the total ratio of Mn element, Fe element and Cu element). It can be selected from the range, for example, 0.2 to 3 parts by mass (for example, 0.25 to 2 parts by mass), preferably 0.3 to 1.5 parts by mass (for example, 0.35 to 1.4 parts by mass), and more preferably. Is about 0.35 to 1 part by mass, more preferably 0.35 to 0.8 part by mass, and most preferably about 0.4 to 0.6 part by mass. If the proportion of the metal component (C) is too small, the denseness of the fired body may decrease, and if it is too large, the conductivity may decrease.
［樹脂成分（Ｄ）］
本発明の導電性組成物は、有機バインダーとして樹脂成分（Ｄ）をさらに含んでいてもよい。樹脂成分としては、特に限定されず、例えば、熱可塑性樹脂（オレフィン系樹脂、ビニル系樹脂、アクリル系樹脂、スチレン系樹脂、ポリエーテル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、セルロース誘導体など）、熱硬化性樹脂（熱硬化性アクリル系樹脂、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル系樹脂、ポリウレタン系樹脂など）などが挙げられる。これらの樹脂成分は、単独でまたは二種以上組み合わせて使用できる。これらの樹脂成分のうち、焼成過程で容易に焼失し、かつ灰分の少ない樹脂、例えば、アクリル系樹脂（ポリメチルメタクリレート、ポリブチルメタクリレートなど）、セルロース誘導体（ニトロセルロース、エチルセルロース、ブチルセルロース、酢酸セルロースなど）、ポリエーテル類（ポリオキシメチレンなど）、ゴム類（ポリブタジエン、ポリイソプレンなど）などが汎用され、エチルセルロースなどのセルロース誘導体が好ましい。
[Resin component (D)]
The conductive composition of the present invention may further contain the resin component (D) as an organic binder. The resin component is not particularly limited, and for example, a thermoplastic resin (olefin resin, vinyl resin, acrylic resin, styrene resin, polyether resin, polyester resin, polyamide resin, cellulose derivative, etc.), Examples thereof include thermosetting resins (thermosetting acrylic resins, epoxy resins, phenol resins, unsaturated polyester resins, polyurethane resins, etc.). These resin components can be used alone or in combination of two or more. Among these resin components, resins that are easily burned out in the firing process and have a low ash content, such as acrylic resins (polymethylmethacrylate, polybutylmethacrylate, etc.) and cellulose derivatives (nitrocellulose, ethylcellulose, butylcellulose, cellulose acetate) , Etc.), polyethers (polyoxymethylene, etc.), rubbers (polybutadiene, polyisoprene, etc.) and the like are widely used, and cellulose derivatives such as ethyl cellulose are preferable.
樹脂成分（Ｄ）の割合は、金属粒子（Ａ）１００質量部に対して、例えば０．１〜１０質量部、好ましくは０．３〜５質量部、さらに好ましくは０．５〜３質量部（特に１〜２質量部）程度である。樹脂成分（Ｄ）の割合が少なすぎると、導電性組成物の取り扱い性が低下する虞があり、逆に多すぎると、焼成体の緻密性が低下する虞がある。 The ratio of the resin component (D) is, for example, 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the metal particles (A). (Especially 1 to 2 parts by mass). If the proportion of the resin component (D) is too small, the handleability of the conductive composition may decrease, and conversely, if it is too large, the denseness of the fired body may decrease.
［有機溶剤（Ｅ）］
有機溶剤（Ｅ）としては、特に限定されず、導電性組成物（特にペースト状組成物）に適度な粘性を付与し、かつ導電性組成物を基板に塗布した後に乾燥処理によって容易に揮発できる有機化合物であればよく、高沸点の有機溶剤であってもよい。
[Organic solvent (E)]
The organic solvent (E) is not particularly limited, and can impart appropriate viscosity to the conductive composition (particularly the paste-like composition), and can be easily volatilized by a drying treatment after the conductive composition is applied to the substrate. It may be an organic compound or an organic solvent having a high boiling point.
このような有機溶剤としては、例えば、芳香族炭化水素（パラキシレン、エチルベンゼン、トリメチルベンゼン、ナフタレン、クメン、インデンなど）、脂肪族炭化水素（ヘキサン、ヘプタン、オクタン、ノナンなど）、エステル類（乳酸エチル、テキサノールなど）、ケトン類（イソホロンなど）、アミド類（ジメチルホルムアミドなど）、脂肪族アルコール（オクタノール、２−エチルヘキサノール、デカノール、ジアセトンアルコールなど）、セロソルブ類（メチルセロソルブ、エチルセロソルブなど）、セロソルブアセテート類（エチルセロソルブアセテート、ブチルセロソルブアセテートなど）、カルビトール類（カルビトール、メチルカルビトール、エチルカルビトール、ブチルカルビトールなど）、カルビトールアセテート類（エチルカルビトールアセテート、ブチルカルビトールアセテート）、脂肪族多価アルコール類（エチレングリコール、ジエチレングリコール、ジプロピレングリコール、ブタンジオール、トリエチレングリコール、グリセリンなど）、脂環族アルコール類［例えば、シクロヘキサノールなどのシクロアルカノール類；α−テルピネオール、ジヒドロテルピネオールなどのテルペンアルコール類（モノテルペンアルコールなど）など］、芳香族アルコール類（メタクレゾールなど）、芳香族カルボン酸エステル類（ジブチルフタレート、ジオクチルフタレートなど）、窒素含有複素環化合物（ジメチルイミダゾール、ジメチルイミダゾリジノンなど）などが挙げられる。これらの有機溶剤は、単独でまたは二種以上組み合わせて使用できる。 Examples of such organic solvents include aromatic hydrocarbons (paraxylene, ethylbenzene, trimethylbenzene, naphthalene, cumene, inden, etc.), aliphatic hydrocarbons (hexane, heptane, octane, nonane, etc.), esters (lactic acid). Ethyl, texanol, etc.), ketones (isophorone, etc.), amides (dimethylformamide, etc.), aliphatic alcohols (octanol, 2-ethylhexanol, decanol, diacetone alcohol, etc.), cellosolves (methylcellosolve, ethylcellosolve, etc.) , Cellosolve acetates (ethyl cellosolve acetate, butyl cellosolve acetate, etc.), carbitols (carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, etc.), carbitol acetates (ethyl carbitol acetate, butyl carbitol acetate) , Aliphatic polyhydric alcohols (ethylene glycol, diethylene glycol, dipropylene glycol, butanediol, triethylene glycol, glycerin, etc.), alicyclic alcohols [eg, cycloalkanols such as cyclohexanol; α-terpineol, dihydroterpineol Terpen alcohols (monoterpene alcohol, etc.), etc.], aromatic alcohols (methacresol, etc.), aromatic carboxylic acid esters (dibutylphthalate, dioctylphthalate, etc.), nitrogen-containing heterocyclic compounds (dimethylimidazole, dimethylimidazole, etc.) Riginon etc.) and so on. These organic solvents can be used alone or in combination of two or more.
これらの有機溶剤のうち、導電性組成物の流動性などの点から、テキサノール（２,２,４−トリメチルペンタン−１,３−ジオールモノイソブチラート）などの脂肪族ジオールモノカルボキシレート、オクタノールなどの脂肪族アルコール、テルピネオールなどの脂環族アルコール、ブチルカルビトールなどのカルビトール類、ブチルカルビトールアセテートなどのカルビトールアセテート類が好ましく、前記脂肪族ジオールモノカルボキシレートと前記カルビトールアセテート類との組み合わせが特に好ましい。前記脂肪族ジオールモノカルボキシレートと前記カルビトールアセテート類とを組み合わせる場合、両者の質量比は、前者／後者＝９９／１〜１０／９０、好ましくは９０／１０〜３０／７０、さらに好ましくは８０／２０〜５０／５０（特に７５／２５〜６０／４０）程度である。さらに、有機溶媒は、耐めっき性を向上できる点からは、芳香族炭化水素や脂肪族炭化水素などの石油系炭化水素（またはミネラルスピリット）などの炭化水素類が好ましい。 Among these organic solvents, aliphatic diol monocarboxylates such as texanol (2,2,4-trimethylpentane-1,3-diol monoisobutyrate) and octanol are considered from the viewpoint of fluidity of the conductive composition. Aliphatic alcohols such as, alicyclic alcohols such as terpineol, carbitols such as butyl carbitol, and carbitol acetates such as butyl carbitol acetate are preferable, and the aliphatic diol monocarboxylate and the carbitol acetates are used. The combination of is particularly preferable. When the aliphatic diol monocarboxylate and the carbitol acetates are combined, the mass ratio of the two is the former / the latter = 99/1 to 10/90, preferably 90/10 to 30/70, and more preferably 80. It is about / 20 to 50/50 (particularly 75/25 to 60/40). Further, as the organic solvent, hydrocarbons such as petroleum-based hydrocarbons (or mineral spirits) such as aromatic hydrocarbons and aliphatic hydrocarbons are preferable from the viewpoint of improving plating resistance.
有機溶剤（Ｅ）の割合は、金属粒子（Ａ）１００質量部に対して０．０１〜５０質量部程度の範囲から選択でき、例えば１〜３０質量部、好ましくは３〜２０質量部、さらに好ましくは５〜１５質量部（特に８〜１３質量部）程度である。有機溶剤（Ｅ）が石油系炭化水素を含む場合、石油系炭化水素の割合は、金属粒子（Ａ）１００質量部に対して、例えば０．０１〜３０質量部、好ましくは０．０５〜２０質量部、さらに好ましくは０．１〜１０質量部、より好ましくは０．５〜５質量部、最も好ましくは１〜３質量部である。有機溶剤（Ｅ）の割合が少なすぎると、導電性組成物の粘度が上昇して取り扱い性および耐めっき性が低下する虞があり、逆に多すぎると、焼成体の緻密性が低下する虞がある。 The ratio of the organic solvent (E) can be selected from the range of about 0.01 to 50 parts by mass with respect to 100 parts by mass of the metal particles (A), for example, 1 to 30 parts by mass, preferably 3 to 20 parts by mass, and further. It is preferably about 5 to 15 parts by mass (particularly 8 to 13 parts by mass). When the organic solvent (E) contains a petroleum-based hydrocarbon, the ratio of the petroleum-based hydrocarbon is, for example, 0.01 to 30 parts by mass, preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the metal particles (A). It is by mass, more preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and most preferably 1 to 3 parts by mass. If the proportion of the organic solvent (E) is too small, the viscosity of the conductive composition may increase and the handleability and plating resistance may decrease. On the contrary, if the proportion of the organic solvent (E) is too large, the denseness of the fired body may decrease. There is.
［他の金属含有成分（Ｆ）］
本発明の導電性組成物は、前記金属粒子（Ａ）および前記金属成分（Ｃ）以外の金属含有成分（他の金属含有成分）（Ｆ）をさらに含んでいてもよい。
[Other metal-containing components (F)]
The conductive composition of the present invention may further contain a metal-containing component (other metal-containing component) (F) other than the metal particles (A) and the metal component (C).
他の金属含有成分（Ｆ）としては、例えば、Ｐｄ、Ａｌ、Ｎｉ、Ｍｏ、Ｗ、Ｐｔ、Ａｕ、Ｃｏ、Ｔｉ、Ｚｒ、Ｓｎなどからなる群から選択された金属元素の金属成分（金属単体、金属化合物）やＡｇ化合物、Ｐｄ、Ａｌなどの前記群およびＭｎ、Ｆｅ、Ｃｕから選択された２種以上の金属元素の合金または複合金属化合物などが挙げられる。 As the other metal-containing component (F), for example, the metal component of the metal element selected from the group consisting of Pd, Al, Ni, Mo, W, Pt, Au, Co, Ti, Zr, Sn and the like (metal simple substance). , Metal compounds), Ag compounds, Pd, Al and the like, and alloys or composite metal compounds of two or more metal elements selected from Mn, Fe and Cu.
他の金属含有成分の形状は、好ましい態様も含め、前記金属粒子（Ａ）と同一である。 The shape of the other metal-containing component is the same as that of the metal particle (A), including the preferred embodiment.
他の金属含有成分（Ｆ）で形成された粒子の粒径は、特に限定されず、中心粒径（Ｄ５０）として０．５〜３０μｍ程度の範囲から選択でき、中心粒径は、例えば１〜１０μｍ、好ましくは１〜４μｍ、さらに好ましくは１．５〜３μｍ（特に１．５〜２．５μｍ）程度である。中心粒径が小さすぎると、セラミックス基板に対する密着性が低下する虞があり、逆に大きすぎても、同様に密着性が低下する虞がある。 The particle size of the particles formed by the other metal-containing component (F) is not particularly limited, and the center particle size (D50) can be selected from the range of about 0.5 to 30 μm, and the center particle size is, for example, 1 to 1. It is about 10 μm, preferably 1 to 4 μm, and more preferably 1.5 to 3 μm (particularly 1.5 to 2.5 μm). If the centriole particle size is too small, the adhesion to the ceramic substrate may decrease, and conversely, if it is too large, the adhesion may decrease as well.
他の金属含有成分（Ｆ）の割合は、金属元素換算で、金属粒子（Ａ）１００質量部に対して５質量部以下（例えば０．０１〜５質量部）程度であってもよい。 The ratio of the other metal-containing component (F) may be about 5 parts by mass or less (for example, 0.01 to 5 parts by mass) with respect to 100 parts by mass of the metal particles (A) in terms of metal elements.
本発明の導電性組成物は、耐めっき性を向上できる点から、チタン化合物を実質的に含まないのが好ましく、チタン化合物を含まないのが特に好ましい。 The conductive composition of the present invention preferably contains substantially no titanium compound, and particularly preferably does not contain a titanium compound, from the viewpoint of improving plating resistance.
［慣用の添加剤］
本発明の導電性組成物は、本発明の効果を損なわない範囲で、慣用の添加剤をさらに含んでいてもよい。慣用の添加剤としては、例えば、硬化剤（アクリル系樹脂の硬化剤など）、着色剤（染顔料など）、色相改良剤、染料定着剤、光沢付与剤、金属腐食防止剤、安定剤（酸化防止剤、紫外線吸収剤など）、界面活性剤または分散剤（アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤など）、分散安定化剤、粘度調整剤またはレオロジー調整剤、保湿剤、チクソトロピー性賦与剤、レベリング剤、消泡剤、殺菌剤、充填剤などが挙げられる。これらの他の成分は、単独でまたは二種以上組み合わせて使用できる。慣用の添加剤の合計割合は、成分の種類に応じて選択でき、通常、金属粒子（Ａ）１００質量部に対して１０質量部以下（例えば０．０１〜１０質量部）程度である。
[Conventional Additives]
The conductive composition of the present invention may further contain conventional additives as long as the effects of the present invention are not impaired. Conventional additives include, for example, hardeners (hardeners for acrylic resins, etc.), colorants (dye pigments, etc.), hue improvers, dye fixers, gloss enhancers, metal corrosion inhibitors, stabilizers (oxidation). Inhibitors, UV absorbers, etc.), Surfactants or Dispersants (Anionic Surfactants, Cationic Surfactants, Nonionic Surfactants, Amphoteric Surfactants, etc.), Dispersion Stabilizers, Viscosity Adjusters or Examples include rheology modifiers, moisturizers, thixotropic agents, leveling agents, defoamers, bactericides, fillers and the like. These other ingredients can be used alone or in combination of two or more. The total ratio of the conventional additives can be selected according to the type of the component, and is usually about 10 parts by mass or less (for example, 0.01 to 10 parts by mass) with respect to 100 parts by mass of the metal particles (A).
［導電性組成物の調製方法］
本発明の導電性組成物（または導電性ペースト）の調製方法としては、各成分を均一に分散させるため、慣用の混合機を用いて混合する方法などを利用でき、粉砕機能を有する装置（例えば、３本ロール、乳鉢、ミルなど）を使用してもよい。各成分の添加方法は、一括添加して混合する方法であってもよく、分割して添加して混合する方法であってもよい。
[Method for preparing conductive composition]
As a method for preparing the conductive composition (or conductive paste) of the present invention, a method of mixing using a conventional mixer or the like can be used in order to uniformly disperse each component, and an apparatus having a pulverizing function (for example,). , 3 rolls, mortar, mill, etc.) may be used. The method of adding each component may be a method of collectively adding and mixing, or a method of dividing and adding and mixing.
本発明では、耐めっき性を向上できる点から、前記有機金属化合物を液状組成物の形態で添加するのが好ましく、前記Ｍｎ成分（Ｃ１）、前記Ｆｅ成分（Ｃ２）および前記Ｃｕ成分（Ｃ３）からなる群より選択された少なくとも１種を液状組成物の形態で添加するのがさらに好ましく、少なくとも前記Ｍｎ成分（Ｃ１）を液状組成物の形態で添加するのが特に好ましい。 In the present invention, it is preferable to add the organometallic compound in the form of a liquid composition from the viewpoint of improving plating resistance, and the Mn component (C1), the Fe component (C2) and the Cu component (C3). It is more preferable to add at least one selected from the group consisting of the above in the form of a liquid composition, and it is particularly preferable to add at least the Mn component (C1) in the form of a liquid composition.
［メタライズド基板およびその製造方法］
本発明のメタライズド基板（配線回路基板などの導電部付セラミックス基板）は、セラミックス基板に前記導電性組成物を付着させる付着工程、前記セラミックス基板に付着した前記導電性組成物を焼成して導電部を形成する焼成工程を経て得られる。
[Metalized substrate and its manufacturing method]
The metallized substrate (ceramic substrate with a conductive portion such as a wiring circuit board) of the present invention has a bonding step of adhering the conductive composition to the ceramic substrate, and the conductive composition adhered to the ceramic substrate is fired to form the conductive portion. It is obtained through a firing step of forming.
付着工程において、導電性組成物の付着方法は、メタライズド基板の種類に応じて選択でき、表面メタライズド基板やスルーホール壁面メタライズド基板では、基板の表面や貫通孔（スルーホール）の内壁に導電性組成物を塗布してもよく、ビア充填基板では表裏貫通穴に対して導電性組成物を充填（ビア充填）してもよい。 In the bonding step, the method of bonding the conductive composition can be selected according to the type of the metallized substrate. In the surface metallized substrate and the through-hole wall surface metallized substrate, the conductive composition is formed on the surface of the substrate and the inner wall of the through hole (through hole). An object may be applied, and in the via-filled substrate, the conductive composition may be filled (via-filled) in the front and back through holes.
導電性組成物を用いて塗膜を形成する方法としては、慣用のコーティング方法、例えば、フローコーティング法、ディスペンサーコーティング法、スピンコーティング法、スプレーコーティング法、スクリーン印刷法、フレキソ印刷法、キャスト法、バーコーティング法、カーテンコーティング法、ロールコーティング法、グラビアコーティング法、ディッピング法、スリット法、フォトリソグラフィ法、インクジェット法などを利用できる。前記コーティング方法において、塗膜でパターンを形成（描画）してもよく、形成されたパターン（描画パターン）を乾燥することによりパターン（焼結膜、金属膜、焼結体層、導体層）を形成できる。パターン（塗布層）を描画するための描画法（または印刷法）としては、パターン形成可能な印刷法であれば特に限定されず、例えば、スクリーン印刷法、インクジェット印刷法、凹版印刷法（例えば、グラビア印刷法など）、オフセット印刷法、凹版オフセット印刷法、フレキソ印刷法などが挙げられる。これらのうち、スクリーン印刷法が好ましい。 As a method for forming a coating film using a conductive composition, conventional coating methods such as flow coating method, dispenser coating method, spin coating method, spray coating method, screen printing method, flexographic printing method, casting method, etc. A bar coating method, a curtain coating method, a roll coating method, a gravure coating method, a dipping method, a slit method, a photolithography method, an inkjet method, etc. can be used. In the coating method, a pattern may be formed (drawn) with a coating film, and a pattern (sintered film, metal film, sintered body layer, conductor layer) is formed by drying the formed pattern (drawing pattern). it can. The drawing method (or printing method) for drawing the pattern (coating layer) is not particularly limited as long as it is a printing method capable of forming a pattern, and for example, a screen printing method, an inkjet printing method, or an intaglio printing method (for example,). Gravure printing method, etc.), offset printing method, intaglio offset printing method, flexo printing method, etc. Of these, the screen printing method is preferable.
セラミックス基板の材質としては、例えば、金属酸化物（アルミナまたは酸化アルミニウム、ジルコニア、サファイア、フェライト、酸化亜鉛、酸化ニオブ、ムライト、ベリリアなど）、酸化ケイ素（石英、二酸化ケイ素など）、金属窒化物（窒化アルミニウム、窒化チタンなど）、窒化ケイ素、窒化ホウ素、窒化炭素、金属炭化物（炭化チタン、炭化タングステンなど）、炭化ケイ素、炭化ホウ素、金属複酸化物［チタン酸金属塩（チタン酸バリウム、チタン酸ストロンチウム、チタン酸鉛、チタン酸ニオブ、チタン酸カルシウム、チタン酸マグネシウムなど）、ジルコン酸金属塩（ジルコン酸バリウム、ジルコン酸カルシウム、ジルコン酸鉛など）など］などが挙げられる。これらのセラミックスは単独でまたは二種以上組み合わせて使用できる。 Examples of the material of the ceramic substrate include metal oxides (alumina or aluminum oxide, zirconia, sapphire, ferrite, zinc oxide, niobium oxide, mulite, beryllia, etc.), silicon oxide (quartz, silicon dioxide, etc.), and metal nitrides (metal nitrides, etc.). Aluminum oxide, titanium nitride, etc.), silicon nitride, boron nitride, carbon nitride, metal carbides (titanium carbide, tungsten carbide, etc.), silicon carbide, boron carbide, metal compound oxide [metal salt titanate (barium titanate, titanic acid, etc.) Strontium, lead titanate, niobium titanate, calcium titanate, magnesium titanate, etc.), metal dilcone acid salts (barium zirconate, calcium zirconate, lead zirconate, etc.), etc.] and the like. These ceramics can be used alone or in combination of two or more.
これらのセラミックス基板のうち、電気電子分野で信頼性が高い点から、アルミナ基板、アルミナ−ジルコニア基板、窒化アルミニウム基板、窒化ケイ素基板、炭化ケイ素基板が好ましく、アルミナ基板、窒化アルミニウム基板、窒化ケイ素基板が特に好ましい。 Among these ceramic substrates, alumina substrates, alumina-zirconia substrates, aluminum nitride substrates, silicon nitride substrates, and silicon carbide substrates are preferable from the viewpoint of high reliability in the field of electricity and electronics, and alumina substrates, aluminum nitride substrates, and silicon nitride substrates are preferable. Is particularly preferable.
セラミックス基板の厚みは、用途に応じて適宜選択すればよく、例えば０．００１〜１０ｍｍ、好ましくは０．０１〜５ｍｍ、さらに好ましくは０．０５〜３ｍｍ（特に０．１〜１ｍｍ）程度であってもよい。 The thickness of the ceramic substrate may be appropriately selected depending on the intended use, and is, for example, 0.001 to 10 mm, preferably 0.01 to 5 mm, and more preferably 0.05 to 3 mm (particularly 0.1 to 1 mm). You may.
焼成における雰囲気は、空気中が好ましい。焼成温度は、導電性組成物中のガラス粒子の軟化点を超えていればよく、例えば６００〜１１００℃、好ましくは７００〜１０００℃、さらに好ましくは８００〜９５０℃程度である。焼成時間は、例えば１分〜３時間、好ましくは１０分〜２時間、さらに好ましくは３０分〜１．５時間程度である。 The atmosphere in firing is preferably in air. The firing temperature may exceed the softening point of the glass particles in the conductive composition, and is, for example, 600 to 1100 ° C., preferably 700 to 1000 ° C., and more preferably about 800 to 950 ° C. The firing time is, for example, 1 minute to 3 hours, preferably 10 minutes to 2 hours, and more preferably about 30 minutes to 1.5 hours.
焼成（特に窒素雰囲気中での焼成）は、バッチ炉またはベルト搬送式のトンネル炉を用いて行ってもよい。 The firing (particularly firing in a nitrogen atmosphere) may be performed using a batch furnace or a belt-conveying tunnel furnace.
本発明のメタライズド基板は、導電性に優れており、導電部の抵抗値は５μΩｃｍ以下（例えば１〜５μΩｃｍ）であってもよい。 The metallized substrate of the present invention has excellent conductivity, and the resistance value of the conductive portion may be 5 μΩcm or less (for example, 1 to 5 μΩcm).
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。以下の例において、実施例で使用した材料、実施例で得られた評価用基板、得られた基板の評価方法を以下に示す。 Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. In the following examples, the materials used in the examples, the evaluation substrate obtained in the examples, and the evaluation method of the obtained substrate are shown below.
［使用した材料］
（Ａｇ粒子）
球状Ａｇ粒子（２μｍ）…中心粒径Ｄ５０：約２μｍ、比表面積０．４０ｍ２／ｇ
（ＡｇＰｄ粒子）
ＡｇＰｄ粒子（Ｐｄ５％）…ＡｇとＰｄとの合金粒子（ＡｇとＰｄとの質量比：Ａｇ／Ｐｄ＝９５／５）、球状、中心粒径Ｄ５０：約１．２μｍ、比表面積１．１ｍ２／ｇ
（ガラス粒子）
シリカ系ガラス粒子…組成ＳｉＯ２−Ｂ２Ｏ３−ＲＯ、軟化温度７８０℃
亜鉛系ガラス粒子…組成ＺｎＯ−ＳｉＯ２−Ｂ２Ｏ３−ＲＯ、軟化温度５７５℃
ビスマス系ガラス粒子…組成Ｂｉ２Ｏ３−ＺｎＯ−Ｂ２Ｏ３、軟化温度４９０℃
（金属成分）
酸化マンガン（ＭｎＯ）粒子…純度３Ｎ、平均粒径：約５〜１０μｍ
Ｍｎ系金属石鹸（オクチル酸マンガン）…オクチル酸マンガン（II）ミネラルスピリット溶液、マンガン含量８質量％
酸化鉄（Ｆｅ２Ｏ３）粒子…純度２Ｎ、平均粒径：約１μｍ
Ｆｅ系金属石鹸（オクチル酸鉄）…オクチル酸鉄ミネラルスピリット溶液、鉄含量６質量％
酸化銅（ＣｕＯ）粒子…純度３Ｎ、平均粒径：約１μｍ
銅粉…中心粒径Ｄ５０：約１．１μｍ
Ｃｕ系金属石鹸（ナフテン酸銅）…ナフテン酸銅ミネラルスピリット溶液、銅含量８質量％
Ｚｎ系金属石鹸（オクチル酸亜鉛）…オクチル酸亜鉛ミネラルスピリット溶液、亜鉛含量８質量％
酸化チタン…平均粒径Ｄ５０：０．２５μｍ、球状
（樹脂成分）
エチルセルロース…ダウケミカル（株）製「ＳＴＤ２０」。
[Material used]
(Ag particles)
Spherical Ag particles (2 μm) ... Center particle size D50: Approximately 2 μm, specific surface area 0.40 m 2 / g
(AgPd particles)
AgPd particles (Pd5%) ... Alloy particles of Ag and Pd (mass ratio of Ag and Pd: Ag / Pd = 95/5), spherical, central particle size D50: about 1.2 μm, specific surface area 1.1 m 2 / G
(Glass particles)
Silica-based glass particles: Composition SiO 2- B 2 O 3- RO, softening temperature 780 ° C.
Zinc-based glass particles: Composition ZnO-SiO 2- B 2 O 3- RO, softening temperature 575 ° C
Bismuth-based glass particles: Composition Bi 2 O 3- ZnO-B 2 O 3 , softening temperature 490 ° C.
(Metal component)
Manganese oxide (MnO) particles: Purity 3N, average particle size: about 5-10 μm
Mn-based metal soap (manganese octylate) ... Manganese octylate (II) mineral spirit solution, manganese content 8% by mass
Iron oxide (Fe 2 O 3 ) particles ... Purity 2N, average particle size: about 1 μm
Fe-based metal soap (iron octylate) ... Iron octylate mineral spirit solution, iron content 6% by mass
Copper oxide (CuO) particles: Purity 3N, average particle size: about 1 μm
Copper powder ... Center particle size D50: Approximately 1.1 μm
Cu-based metal soap (copper naphthenate) ... Copper naphthenate mineral spirit solution, copper content 8% by mass
Zn-based metal soap (zinc octylate) ... Zinc mineral spirit solution, zinc content 8% by mass
Titanium oxide: Average particle size D50: 0.25 μm, spherical (resin component)
Ethyl cellulose ... "STD20" manufactured by Dow Chemical Co., Ltd.
［評価用基板の作製］
表１〜４に示す組成にて実施例１〜１２および比較例１〜１５の導電性ペーストを調製した。ペーストの調製方法としては、テキサノール／ブチルカルビトールアセテート＝５５／３５（質量比）の混合溶媒に、１０質量％のエチルセルロースを溶解した有機ビヒクルと、表１〜４に示す無機成分とを混合してペーストを調製した。その際に、導電性ペースト中の無機成分の固形分濃度が８７質量％となるよう調整した。そして、作製したペーストを用いて、スクリーン印刷で、３インチ×３インチ×０．６３５ｍｍ厚みのアルミナ基板上に、電極を形成し、９００℃、大気下で焼成して評価用基板を作製した。
[Preparation of evaluation board]
Conductive pastes of Examples 1 to 12 and Comparative Examples 1 to 15 were prepared with the compositions shown in Tables 1 to 4. As a method for preparing the paste, an organic vehicle in which 10% by mass of ethyl cellulose is dissolved in a mixed solvent of texanol / butylcarbitol acetate = 55/35 (mass ratio) and the inorganic components shown in Tables 1 to 4 are mixed. The paste was prepared. At that time, the solid content concentration of the inorganic component in the conductive paste was adjusted to 87% by mass. Then, using the prepared paste, electrodes were formed on an alumina substrate having a thickness of 3 inches × 3 inches × 0.635 mm by screen printing, and fired at 900 ° C. in the air to prepare an evaluation substrate.
［初期判定］
（耐硫化性試験）
雰囲気温度４０℃、相対湿度９０％、Ｈ２Ｓ濃度が２．０ｐｐｍおよびＮＯ２濃度が４．０ｐｐｍに調整された混合ガスの環境下に４５０時間放置し、耐硫化試験を行い、以下の基準で判定した。
[Initial judgment]
(Sulfide resistance test)
Atmospheric temperature 40 ° C., a relative humidity of 90%, H 2 S concentration was left 450 hours in an environment of a gas mixture 2.0ppm and NO 2 concentration was adjusted to 4.0 ppm, performs sulfidation test, following criteria Judged by.
〇：全く硫化点がみられないか、または少しみられる
×：全体的に硫化している
〇: No sulfurization point or slight sulfurization point ×: Overall sulfurization
（耐めっき性、初期接着強度）
無電解めっき（Ｎｉ／Ｐｄ／Ａｕ）後、２ｍｍ角パッドパターン部で密着力を評価した。２ｍｍ角パッド表面に沿うように錫メッキ軟銅線（ピール線）をハンダ付けした。このとき、銅線を持ち上げただけで電極が剥がれたものは、耐めっき性評価×とした。
(Plating resistance, initial adhesive strength)
After electroless plating (Ni / Pd / Au), the adhesion was evaluated at the 2 mm square pad pattern portion. A tin-plated annealed copper wire (peel wire) was soldered along the surface of the 2 mm square pad. At this time, if the electrode was peeled off just by lifting the copper wire, the plating resistance evaluation was ×.
パッド端に位置する箇所において軟銅線を垂直上方に折り曲げたものを引張試験機に固定し、パッドが基板から剥離するまで引張上げた。パッドが基板から剥離する際の最も高い荷重をピール強度（２ｍｍパターンのピール強度）として記録した。得られたピール強度について、以下の基準で評価した。ピール強度が３ｋｇｆ以上とは、パターン１ｍｍあたりのピール強度が０．７５ｋｇｆ以上であることを意味し、銅線を持ち上げただけで電極が剥がれたものは、０ｋｇｆとした。 An annealed copper wire bent vertically upward at a position located at the end of the pad was fixed to a tensile tester and pulled up until the pad was peeled off from the substrate. The highest load when the pad peeled from the substrate was recorded as the peel strength (2 mm pattern peel strength). The obtained peel strength was evaluated according to the following criteria. The peel strength of 3 kgf or more means that the peel strength per 1 mm of the pattern is 0.75 kgf or more, and the case where the electrode is peeled off only by lifting the copper wire is set to 0 kgf.
◎：３ｋｇｆ以上
○：２ｋｇｆ以上３ｋｇｆ未満
×：２ｋｇｆ未満。
⊚: 3 kgf or more ○: 2 kgf or more and less than 3 kgf ×: less than 2 kgf.
（比抵抗）
比抵抗は、四探針法での表面抵抗と膜厚とから算出した。実施例および比較例で得られた導電膜について、それぞれ１０サンプルの測定を行い、その平均値を求めた。
(Specific resistance)
The specific resistance was calculated from the surface resistance and the film thickness in the four-probe method. For each of the conductive films obtained in Examples and Comparative Examples, 10 samples were measured, and the average value was calculated.
（初期判定の判定方法）
上記評価試験の結果について、初期判定として、以下の基準で判定し、ランク付けした。
(Judgment method of initial judgment)
The results of the above evaluation tests were judged and ranked according to the following criteria as initial judgments.
ランクＡ：耐硫化性、耐めっき性が◎と○である（合格）
ランクＢ：耐硫化性、耐めっき性がいずれも○であり、◎がない（合格）
ランクＣ：耐硫化性、耐めっき性に×がある（不合格）
Rank A: Sulfurization resistance and plating resistance are ◎ and ○ (pass)
Rank B: Sulfurization resistance and plating resistance are both ○ and no ◎ (pass)
Rank C: Sulfurization resistance and plating resistance are x (failed)
［総合判定］
初期判定で合格した基板について以下の信頼性評価を行って総合判定した。
[Comprehensive judgment]
The following reliability evaluation was performed on the substrates that passed the initial judgment to make a comprehensive judgment.
（恒温恒湿試験）
恒温恒湿試験は、温度８５℃、相対湿度８５％ＲＨにした恒温恒湿槽に１０００時間放置した後、焼成膜の密着力（接着強度）を測定し、以下の基準で判定した。
(Constant temperature and humidity test)
In the constant temperature and humidity test, the adhesive strength (adhesive strength) of the fired film was measured after being left in a constant temperature and humidity bath at a temperature of 85 ° C. and a relative humidity of 85% RH for 1000 hours, and the determination was made according to the following criteria.
◎：２ｋｇｆ以上
○：１．５ｋｇｆ以上２ｋｇｆ未満
×：１．５ｋｇｆ未満。
⊚: 2 kgf or more ○: 1.5 kgf or more and less than 2 kgf ×: less than 1.5 kgf.
（ヒートサイクル試験）
−４０℃／１２５℃の１０００サイクル後の接着強度を測定し、以下の基準で判定した。
(Heat cycle test)
The adhesive strength after 1000 cycles at −40 ° C./125 ° C. was measured and judged according to the following criteria.
◎：２ｋｇｆ以上
○：１．５ｋｇｆ以上２ｋｇｆ未満
×：１．５ｋｇｆ未満。
⊚: 2 kgf or more ○: 1.5 kgf or more and less than 2 kgf ×: less than 1.5 kgf.
（熱エージング試験）
１７０℃のオーブンで１０００時間経過後に接着強度を測定し、以下の基準で判定した。
(Heat aging test)
The adhesive strength was measured after 1000 hours in an oven at 170 ° C., and the determination was made according to the following criteria.
◎：２ｋｇｆ以上
○：１．５ｋｇｆ以上２ｋｇｆ未満
×：１．５ｋｇｆ未満。
⊚: 2 kgf or more ○: 1.5 kgf or more and less than 2 kgf ×: less than 1.5 kgf.
（総合判定の判定方法）
上記評価試験の結果について、総合判定として、以下の基準で判定し、ランク付けした。
(Judgment method of comprehensive judgment)
The results of the above evaluation tests were judged and ranked according to the following criteria as a comprehensive judgment.
ランクＡ：信頼性試験が全て◎である（合格）
ランクＢ：信頼性試験が◎と○、あるいは全て○である（合格）
ランクＣ：信頼性試験に×がある、または初期判定でランクＣ（不合格）
Rank A: All reliability tests are ◎ (pass)
Rank B: Reliability test is ◎ and ○, or all ○ (pass)
Rank C: There is a cross in the reliability test, or rank C (failed) in the initial judgment.
実施例１〜１２および比較例１〜１５で得られた評価基板の評価結果を表１〜４に示す。 Tables 1 to 4 show the evaluation results of the evaluation substrates obtained in Examples 1 to 12 and Comparative Examples 1 to 15.
なお、表１〜４において、「Ｐｄの割合」は、Ａｇ粒子およびＡｇＰｄ粒子の総量に対するＰｄの割合（質量％）を意味し（全金属粒子（Ａ）中のＰｄの割合）、「金属成分（Ｃ）の割合」は、Ａｇ粒子およびＡｇＰｄ粒子の総量に対する金属成分（Ｃ）の金属元素換算での割合（質量％）を意味し（金属粒子（Ａ）１００質量部に対する金属成分（Ｃ）に含まれる金属元素の質量部）、「ガラス粒子の割合」は、Ａｇ粒子およびＡｇＰｄ粒子の総量に対するガラス粒子の割合（質量％）を意味する（金属粒子（Ａ）１００質量部に対するガラス粒子（Ｂ）の質量部）。 In Tables 1 to 4, "ratio of Pd" means the ratio (mass%) of Pd to the total amount of Ag particles and AgPd particles (ratio of Pd in all metal particles (A)), and "metal component". "Ratio of (C)" means the ratio (mass%) of the metal component (C) to the total amount of Ag particles and AgPd particles in terms of metal element (metal component (C) with respect to 100 parts by mass of the metal particles (A)). "Ratio of glass particles to the total amount of Ag particles and AgPd particles" means the ratio (% by mass) of the glass particles to 100 parts by mass of the metal particles (A). B) Mass part).
表１〜４の結果から明らかなように、実施例で得られた基板では、耐めっき性が高く、使用環境変化に拘わらず信頼性が高いのに対して、比較例で得られた基板は耐めっき性が低かった。 As is clear from the results in Tables 1 to 4, the substrates obtained in the examples have high plating resistance and high reliability regardless of changes in the usage environment, whereas the substrates obtained in the comparative examples have high plating resistance. The plating resistance was low.
さらに、表１の結果から明らかなように、Ｍｎ成分（Ｃ１）、Ｆｅ成分（Ｃ２）、Ｃｕ成分（Ｃ３）の種類に関して、金属成分のうち、少なくとも１種類が有機金属化合物を含む液状組成物の場合に耐めっき性が得られる（実施例１〜６）。一方、いずれの金属成分も無機金属化合物である比較例１は、耐めっき性が不充分であった。また、Ｃｕ成分に関しては、Ｃｕ単体でもＣｕ化合物と同様の効果が得られた（実施例３、４、６）。特に、実施例３がバランスに優れた結果を示した。さらに、実施例３に対して、Ａｇ粒子（Ａ１）を含まない比較例２では密着性の不足により耐めっき性が不充分となり、ＡｇＰｄ複合粒子（Ａ２）を含まない比較例３では耐硫化性が不充分となり、両者の併用が必須であると云える。実施例３の結果については、表１だけでなく、表３および４においても、比較のために記載した。 Further, as is clear from the results in Table 1, regarding the types of the Mn component (C1), Fe component (C2), and Cu component (C3), at least one of the metal components is a liquid composition containing an organometallic compound. In the case of (Examples 1 to 6), plating resistance can be obtained. On the other hand, Comparative Example 1 in which all the metal components were inorganic metal compounds had insufficient plating resistance. Regarding the Cu component, the same effect as that of the Cu compound was obtained with Cu alone (Examples 3, 4, and 6). In particular, Example 3 showed excellently balanced results. Further, as compared with Example 3, in Comparative Example 2 containing no Ag particles (A1), the plating resistance became insufficient due to insufficient adhesion, and in Comparative Example 3 containing no AgPd composite particles (A2), sulfurization resistance was insufficient. Is insufficient, and it can be said that the combined use of both is essential. The results of Example 3 are shown for comparison not only in Table 1 but also in Tables 3 and 4.
表２の結果から明らかなように、Ｍｎ成分（Ｃ１）、Ｆｅ成分（Ｃ２）、Ｃｕ成分（Ｃ３）を全く含まない比較例４、１種類のみ含む比較例５〜７、２種類のみ含む比較例８〜１０は、電極が全く密着しないため、耐めっき性で不合格であった。また、３種類のうち、１種類を他の金属成分（Ｚｎ成分、Ｔｉ成分）に変えた比較例１１〜１４も、電極の密着性が得られず耐めっき性で不合格であった。 As is clear from the results in Table 2, Comparative Examples 4 containing no Mn component (C1), Fe component (C2), and Cu component (C3), Comparative Examples 5 to 7 containing only one type, and comparison containing only two types. Examples 8 to 10 failed in plating resistance because the electrodes did not adhere to each other at all. Further, in Comparative Examples 11 to 14 in which one of the three types was changed to another metal component (Zn component, Ti component), the adhesion of the electrodes could not be obtained and the plating resistance was unacceptable.
表３の結果から明らかなように、実施例３に対して、金属成分（Ｃ）の割合を変量した実施例７〜９、比較例１５の結果から、金属成分の割合が０．５質量％（実施例３）程度の場合が特に好ましい。割合を減らした実施例７（０．３質量％）では耐めっき性が低下した。割合を増やした実施例８（１．３質量％）、実施例９（２．４質量％）では耐めっき性が低下し、比較例１５（３．３質量％）では、耐めっき性が得られなくなる（全く密着しない）。 As is clear from the results in Table 3, from the results of Examples 7 to 9 and Comparative Example 15 in which the ratio of the metal component (C) was varied with respect to Example 3, the ratio of the metal component was 0.5% by mass. The case of (Example 3) is particularly preferable. In Example 7 (0.3% by mass) in which the ratio was reduced, the plating resistance was lowered. In Example 8 (1.3% by mass) and Example 9 (2.4% by mass) in which the proportion was increased, the plating resistance was lowered, and in Comparative Example 15 (3.3% by mass), the plating resistance was obtained. It becomes impossible (it does not adhere at all).
表４の結果から明らかなように、実施例１０〜１１は、実施例３に対して、ガラス粒子の種類を変えた例であるが、亜鉛系ガラス粒子を用いた実施例１０では実施例３と同等の結果が得られたが、ビスマス系ガラス粒子を用いた実施例１１では密着性の低下により耐めっき性および信頼性が低下した。実施例３に対して、ガラス粒子を増量した実施例１２でも、実施例３と同等の結果が得られた。 As is clear from the results in Table 4, Examples 10 to 11 are examples in which the type of glass particles is changed with respect to Example 3, but in Example 10 using zinc-based glass particles, Example 3 is used. However, in Example 11 using bismuth-based glass particles, the plating resistance and reliability were lowered due to the decrease in adhesion. Even in Example 12 in which the amount of glass particles was increased with respect to Example 3, the same results as in Example 3 were obtained.
本発明の導電性組成物は、回路基板、電子部品、熱基板、ＬＥＤパッケージ用基板、半導体用基板、薄膜回路基板、抵抗器用基板などに利用でき、配線回路基板における電極などの導電部を形成するための組成物として特に有効に利用できる。
The conductive composition of the present invention can be used for circuit boards, electronic components, thermal boards, LED package boards, semiconductor boards, thin film circuit boards, resistor boards, etc., and forms conductive parts such as electrodes in wiring circuit boards. It can be particularly effectively used as a composition for this purpose.
Claims (9)
前記金属粒子（Ａ）が、Ａｇ粒子（Ａ１）ならびにＡｇおよびＰｄの複合粒子（Ａ２）であるとともに、
前記金属成分（Ｃ）が、Ｍｎ成分（Ｃ１）、Ｆｅ成分（Ｃ２）およびＣｕ成分（Ｃ３）であり、かつ前記金属成分（Ｃ）が有機金属化合物を含む導電性組成物。 A conductive composition containing metal particles (A), glass particles (B) and a metal component (C).
The metal particles (A) are Ag particles (A1) and composite particles of Ag and Pd (A2).
A conductive composition in which the metal component (C) is an Mn component (C1), an Fe component (C2) and a Cu component (C3), and the metal component (C) contains an organometallic compound.
The metallized substrate according to claim 8, wherein the ceramic substrate is an alumina substrate, an alumina-zirconia substrate, an aluminum nitride substrate, a silicon nitride substrate, or a silicon carbide substrate.
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| JPH07335402A (en) * | 1994-06-06 | 1995-12-22 | Sumitomo Metal Mining Co Ltd | Paste for forming electrode on chip resistor |
| JP2002231049A (en) * | 2001-01-29 | 2002-08-16 | Daido Steel Co Ltd | Conductive paste |
| JP2005085937A (en) * | 2003-09-08 | 2005-03-31 | Kyocera Corp | Piezoelectric actuator, conductive paste therefor, and liquid discharge apparatus |
| JP2013140991A (en) * | 2006-10-11 | 2013-07-18 | Mitsubishi Materials Corp | Composition for electrode formation and method for forming electrode by using the composition |
| JP2015207629A (en) * | 2014-04-18 | 2015-11-19 | ナミックス株式会社 | Conductive paste, and crystal silicon solar battery |
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| JPH07335402A (en) * | 1994-06-06 | 1995-12-22 | Sumitomo Metal Mining Co Ltd | Paste for forming electrode on chip resistor |
| JP2002231049A (en) * | 2001-01-29 | 2002-08-16 | Daido Steel Co Ltd | Conductive paste |
| JP2005085937A (en) * | 2003-09-08 | 2005-03-31 | Kyocera Corp | Piezoelectric actuator, conductive paste therefor, and liquid discharge apparatus |
| JP2013140991A (en) * | 2006-10-11 | 2013-07-18 | Mitsubishi Materials Corp | Composition for electrode formation and method for forming electrode by using the composition |
| JP2015207629A (en) * | 2014-04-18 | 2015-11-19 | ナミックス株式会社 | Conductive paste, and crystal silicon solar battery |
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