JP5124822B2 - Method for producing composite metal powder and dispersion thereof - Google Patents
Method for producing composite metal powder and dispersion thereof Download PDFInfo
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- JP5124822B2 JP5124822B2 JP2005207990A JP2005207990A JP5124822B2 JP 5124822 B2 JP5124822 B2 JP 5124822B2 JP 2005207990 A JP2005207990 A JP 2005207990A JP 2005207990 A JP2005207990 A JP 2005207990A JP 5124822 B2 JP5124822 B2 JP 5124822B2
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- silver
- composite metal
- particles
- metal powder
- metal
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- 229910052751 metal Inorganic materials 0.000 title claims description 141
- 239000002184 metal Substances 0.000 title claims description 140
- 239000000843 powder Substances 0.000 title claims description 107
- 239000002131 composite material Substances 0.000 title claims description 81
- 239000006185 dispersion Substances 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000002245 particle Substances 0.000 claims description 126
- 229910052709 silver Inorganic materials 0.000 claims description 85
- 239000004332 silver Substances 0.000 claims description 85
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 83
- 239000007788 liquid Substances 0.000 claims description 68
- -1 silver ions Chemical class 0.000 claims description 26
- 238000006722 reduction reaction Methods 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 150000003077 polyols Chemical class 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910001316 Ag alloy Inorganic materials 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 41
- 238000000034 method Methods 0.000 description 39
- 239000002609 medium Substances 0.000 description 32
- 239000003223 protective agent Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 229910052697 platinum Inorganic materials 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 239000002923 metal particle Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 229910000679 solder Inorganic materials 0.000 description 14
- 230000003628 erosive effect Effects 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 10
- 239000011258 core-shell material Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 7
- 239000003350 kerosene Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229940100890 silver compound Drugs 0.000 description 5
- 150000003379 silver compounds Chemical class 0.000 description 5
- 229910001923 silver oxide Inorganic materials 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
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- 239000011362 coarse particle Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
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- 238000003541 multi-stage reaction Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- 239000001307 helium Substances 0.000 description 2
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- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 2
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- 150000003058 platinum compounds Chemical class 0.000 description 2
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- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
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- JTQQDDNCCLCMER-CLFAGFIQSA-N (z)-n-[(z)-octadec-9-enyl]octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCNCCCCCCCC\C=C/CCCCCCCC JTQQDDNCCLCMER-CLFAGFIQSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
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Description
本発明は銀と銀以外の貴金属類（実際には標準電極電位Ｅ0が０．８０Ｖ以上の銀以外の金属Ｘ）との微細な複合金属粉体の製造法、およびその複合金属粉体の分散液の製造法に関する。 The present invention relates to a method for producing a fine composite metal powder of silver and a noble metal other than silver (actually, a metal X other than silver having a standard electrode potential E 0 of 0.80 V or more), and a method for producing the composite metal powder. It relates to a process for the preparation of the dispersion.
固体物質の大きさがｎｍオーダー（ナノメートルオーダー）になると比表面積が非常に大きくなるために、固体でありながら気体や液体の界面が極端に大きくなる。したがって、その表面の特性が固体物質の性質を大きく左右する。金属粒子粉末の場合は、融点がバルク状態のものに比べ劇的に低下することが知られており、そのためにμｍオーダーの粒子に比べて微細な配線の描画が可能になり、しかも低温焼結できる等の利点を具備するようになる。金属粒子粉末の中でも銀粒子粉末は、低抵抗でかつ高い耐候性をもち、金属の価格も他の貴金属と比較して安価であることから、微細な配線幅をもつ次世代の配線材料として特に期待されている。 When the size of the solid substance is in the order of nm (on the order of nanometers), the specific surface area becomes very large, so that the interface between the gas and the liquid becomes extremely large while being solid. Therefore, the properties of the surface greatly influence the properties of the solid substance. In the case of metal particle powder, it is known that the melting point is drastically lower than that in the bulk state, which makes it possible to draw fine wiring compared to particles on the order of μm, and low temperature sintering. It has advantages such as being able to do so. Among the metal particle powders, the silver particle powder has low resistance and high weather resistance, and the price of the metal is low compared with other noble metals, so it is particularly useful as a next-generation wiring material with a fine wiring width. Expected.
しかし、銀粒子粉末を導電材とするさいには次のような問題が指摘されている。
（ａ）インクジェット法等の手法を用いて銀粒子の分散液によって配線を形成した場合には、回路の集積度向上に伴う配線間隔狭小化につれて、配線間でのエレクトロマイグレーションによる回路短絡が起こり易くなる。
（ｂ）銀粒子の分散液またはペーストによって電気的接点を形成した場合には、めっきを行う際にめっき液の浸透により基材が侵食を受ける。
（ｃ）同様に、半田付けを行う際に半田による電気的接点部の銀の拡散が起こることによる回路配線や電気的接点の信頼性低下する。
However, the following problems have been pointed out when using silver particle powder as a conductive material.
(A) When wiring is formed by a dispersion of silver particles using a technique such as an ink jet method, a short circuit due to electromigration between wirings is likely to occur as the wiring interval is narrowed due to improvement in circuit integration. Become.
(B) When an electrical contact is formed with a silver particle dispersion or paste, the substrate is eroded by the penetration of the plating solution during plating.
(C) Similarly, the reliability of circuit wiring and electrical contacts is reduced due to the diffusion of silver in the electrical contact portions due to solder when soldering.
回路配線のエレクトロマイグレーションを抑制する手段としては、銀のエレクトロマイグレーション性を向上させるパラジウムやチタン等を含有させる方法（例えば、特許文献１）、酸化銅ナノ粒子で配線を形成した後、還元性気体の存在下において生起されるプラズマ雰囲気中で配線を銅に還元する方法（例えば、特許文献２）、さらにはインク中にアルカリ金属元素、アルカリ土類金属元素を含まないことによりエレクトロマイグレーションを回避する方法（例えば、特許文献３）等が提案されている。
特許文献１は、ヘリウム等の不活性ガス雰囲気でかつ０．５Ｔｏｒｒ程度の低圧中で金属を蒸発させる方法（いわゆる蒸発法）を開示しており、この方法で得られる銀粒子はエレクトロマイグレーション性が改善されるとされている。得られる粒子は粒径が１０ｎｍ以下で分散液中の分散性が良好であるが、粒子生成にあたり特別な装置が必要である。このため産業用の銀ナノ粒子を大量に合成するには難があることに加えて、ナノ粒子の収率が低く、この方法で得られるナノ粒子粉末は高価となる。 Patent Document 1 discloses a method (so-called evaporation method) for evaporating a metal in an inert gas atmosphere such as helium and a low pressure of about 0.5 Torr. Silver particles obtained by this method have electromigration properties. It is said that it will be improved. The obtained particles have a particle size of 10 nm or less and good dispersibility in the dispersion, but a special apparatus is required for the particle generation. For this reason, in addition to difficulty in synthesizing industrial silver nanoparticles in large quantities, the yield of nanoparticles is low, and the nanoparticle powder obtained by this method is expensive.
特許文献２では、ヘリウム等の不活性ガス雰囲気でかつ０．５Ｔｏｒｒ程度の低圧中で金属を蒸発させる方法（いわゆる蒸発法）で得た酸化銅粒子で配線形成をした後、還元性気体存在下において生起されるプラズマ雰囲気中で銅まで還元して銅系配線を形成している。蒸発法で得られる粒子は粒径が１０ｎｍ以下で分散液中の分散性が良好であるが、特許文献１と同様に粒子生成にあたり特別な装置が必要である。このため産業用の酸化銅ナノ粒子を大量に合成するには難があることに加えて、酸化銅粒子の収率が低く、この方法で得られる粒子粉末は高価となる。また雰囲気調整をしない大気中での焼成ができず、還元性雰囲気かつプラズマ雰囲気を必要とするので焼成にも特別な装置が必要である。 In Patent Document 2, after wiring is formed with copper oxide particles obtained by a method (so-called evaporation method) of evaporating a metal in an inert gas atmosphere such as helium in a low pressure of about 0.5 Torr, in the presence of a reducing gas. The copper-based wiring is formed by reducing to copper in the plasma atmosphere generated in FIG. The particles obtained by the evaporation method have a particle size of 10 nm or less and good dispersibility in the dispersion. However, as in Patent Document 1, a special apparatus is required for particle generation. Therefore, in addition to the difficulty in synthesizing industrial copper oxide nanoparticles in large quantities, the yield of copper oxide particles is low, and the particle powder obtained by this method is expensive. In addition, firing in the air without adjusting the atmosphere is impossible, and a reducing atmosphere and a plasma atmosphere are required. Therefore, a special apparatus is also required for firing.
特許文献３では出発原料を限定し、クエン酸のアンモニウム塩を保護剤とすることにより、インク中にアルカリ金属、アルカリ土類金属を含まないようにしている。しかし、出発原料や還元剤に塩素や硫黄が含まれており、配線やその他電子部品を腐食させる原因となるため好ましくない。また、インク化前に粒子を乾燥させているが、乾燥により粒子が凝集するため分散性が悪化する。 In Patent Document 3, starting materials are limited, and an ammonium salt of citric acid is used as a protective agent so that the ink does not contain alkali metal or alkaline earth metal. However, it is not preferable because the starting material and the reducing agent contain chlorine and sulfur and cause corrosion of wiring and other electronic components. In addition, the particles are dried before being made into ink, but the particles are aggregated by drying, so that dispersibility is deteriorated.
このように、ナノ粒子粉末によって微細な配線や電気的接点形成を目的とした場合に、ａ）耐エレクトロマイグレーション性、ｂ）耐めっき性、ｃ）耐半田喰われ性を同時に改善し、しかも安価で多量生産に適した金属粉末を得ることは容易ではなかった。本発明はこの要求を満たすことを課題としたものである。 Thus, when the purpose is to form fine wiring and electrical contacts with nanoparticle powder, a) electromigration resistance, b) plating resistance, and c) solder erosion resistance are simultaneously improved and inexpensive. Therefore, it was not easy to obtain metal powder suitable for mass production. The present invention aims to satisfy this requirement.
本発明は、銀と銀以外の貴金属類（標準電極電位Ｅ0が０．８０Ｖ以上の銀以外の金属Ｘ）との微細な複合金属粉体を構成することによって前記の課題の解決を図ったものである。 The present invention has solved the above-mentioned problems by constituting a fine composite metal powder of silver and a noble metal other than silver (a metal X other than silver having a standard electrode potential E 0 of 0.80 V or more). Is.
すなわち、本発明は、下記（Ａ）の複合金属粉体の製造法を提供する。
（Ａ）銀と、標準電極電位Ｅ0が０．８０Ｖ以上の銀以外の金属Ｘとの合金の粒子からなり、金属Ｘの重量割合が１〜８０wt％である複合金属粉体であって、当該合金粒子は平均粒径（ＤTEM）が２０ｎｍ以下で且つ結晶粒子径（Ｄｘ）が２０ｎｍ以下である複合金属粉体（合金粉体）。
That is, this invention provides the manufacturing method of the composite metal powder of the following (A).
And (A) silver, a standard electrode potential E 0 is particles of an alloy of the metal X except more silver 0.80 V, the weight ratio of the metal X is a complex metal powder is 1-80 wt%, The alloy particles are composite metal powder (alloy powder) having an average particle diameter (D TEM ) of 20 nm or less and a crystal particle diameter (Dx) of 20 nm or less .
また本発明は、上記（Ａ）の複合金属粉体を液状有機媒体に分散させてなる複合金属粉体分散液の製造法を提供する。 The present invention also provides a method for producing a composite metal powder dispersion obtained by dispersing the composite metal powder (A) in a liquid organic medium.
具体的には上記（Ａ）の複合金属粉体の有利な製造法として、還元剤として機能するアルコールまたはポリオールの１種または２種以上の液中で銀イオンと金属Ｘイオンを銀粒子と金属Ｘ粒子に還元処理するさいに、その還元反応の条件を制御することにより、上記（Ａ）の複合金属粉体を製造する方法を提供する。そのさい、還元処理にあたっては、１分子中に少なくとも１個以上の不飽和結合を有する分子量１００〜１０００のアミン化合物の共存下で還元する。 Specifically, as an advantageous production method of the composite metal powder of the above (A), silver ions and metal X ions are converted into silver particles and metal in one or more liquids of alcohol or polyol that functions as a reducing agent. Provided is a method for producing the composite metal powder of the above (A) by controlling the reduction reaction conditions when reducing the X particles. Thereof the, when reduction treatment, you reduced in the presence of an amine compound having a molecular weight of 100 to 1000 having one or more unsaturated bonds in one molecule.
また、該複合金属粉体の分散液の製造法として、還元剤として機能するアルコールまたはポリオールの１種または２種以上の液中で銀イオンと金属Ｘイオンを銀粒子と金属Ｘ粒子に還元処理するさいに、１分子中に少なくとも１個以上の不飽和結合を有する分子量１００〜１０００のアミン化合物の共存下においてその還元反応の条件を制御することにより、上記（Ａ）の複合金属粉体を製造し、得られた複合金属粉体を沸点６０〜３００℃の非極性もしくは極性の小さい液状有機媒体に分散させる複合金属粉体分散液の製造法を提供する。 Further, as a method for producing a dispersion of the composite metal powder, silver ions and metal X ions are reduced to silver particles and metal X particles in one or more liquids of alcohol or polyol that function as a reducing agent. At the same time, by controlling the conditions for the reduction reaction in the presence of an amine compound having a molecular weight of 100 to 1000 having at least one unsaturated bond in one molecule, the composite metal powder of the above (A) is obtained. prepared to provide the resulting preparation of double coupling metal powder component dispersion liquid Ru composite metal powder is dispersed in a non-polar or less polar liquid organic medium having a boiling point of 60 to 300 ° C..
本発明の複合金属粉体およびその分散液またはペーストは、大気雰囲気中で低温焼結が可能であり、回路配線や電気的接点として用いた場合のａ）耐エレクトロマイグレーション性、ｂ）耐めっき性、およびｃ）耐半田喰われ性が良好である。このため、微細な配線や電気的接点形成に適する。 The composite metal powder and its dispersion or paste of the present invention can be sintered at low temperature in the air atmosphere, and when used as circuit wiring or electrical contact, a) electromigration resistance, b) plating resistance And c) Good resistance to solder erosion. For this reason, it is suitable for fine wiring and electrical contact formation.
本発明は、基本的には平均粒径ＤTEMが２０ｎｍ以下のナノ粒子分野において、銀と銀以外の金属Ｘとの複合化を行うことによって、銀粉末を回路配線に用いた場合のマイグレーションの問題の解決を図ったものであり、加えて、電気的接点として使用した場合の耐めっき性、および耐半田喰われ性の向上を図ったものである。ここで、金属Ｘは標準電極電位Ｅ0が０．８０Ｖ以上の銀以外の金属を意味し、これを本明細書では金属Ｘと呼ぶ。金属Ｘには種々の金属元素が存在するが、本発明の複合金属粉体の用途を考慮すると、白金、パラジウム、金等が挙げられる。複合化のための金属Ｘの配合量としては、いずれの態様においても、金属Ｘの重量割合が１〜８０wt％の範囲であればよい。 In the nanoparticle field where the average particle diameter D TEM is 20 nm or less, the present invention basically performs migration when silver powder is used for circuit wiring by combining silver and a metal X other than silver. This is intended to solve the problem and, in addition, to improve the plating resistance and solder erosion resistance when used as an electrical contact. Here, the metal X means a metal other than silver having a standard electrode potential E 0 of 0.80 V or more, and this is called a metal X in this specification. Various metal elements exist in the metal X, and platinum, palladium, gold and the like can be mentioned in consideration of the use of the composite metal powder of the present invention. As a compounding amount of the metal X for compounding, the weight ratio of the metal X may be in the range of 1 to 80 wt% in any embodiment.
ナノ銀粒子に金属Ｘを複合化する第一の態様として、まずナノ金属Ｘ粒子を混合する態様がある。この場合には、ナノ銀粒子とナノ金属Ｘ粒子を有利に製造できることが必要である。本発明者はナノ銀粒子と貴金属類のナノ粒子を液相法によって有利に製造できることを見い出した。まず、この点について説明する。 As a first aspect of compositing metal X with nanosilver particles, there is an aspect in which nanometal X particles are first mixed. In this case, it is necessary to be able to advantageously produce nano silver particles and nano metal X particles. The present inventor has found that nano silver particles and noble metal nanoparticles can be advantageously produced by a liquid phase method. First, this point will be described.
本発明者は液相法で銀の粒子粉末を製造する試験を重ねてきたが、沸点が８５〜１５０℃のアルコール中で、硝酸銀を、８５〜１５０℃の温度で（蒸発したアルコールを液相に還流させながら）、例えば分子量１００〜４００のアミン化合物からなる保護剤の共存下で還元処理すると、粒径の揃った球状の銀のナノ粒子粉末が得られることを知見し、特願２００５−２６８０５号明細書および図面に記載した。また、沸点が８５℃以上のアルコールまたはポリオール中で、銀化合物（代表的には炭酸銀または酸化銀）を、８５℃以上の温度で、例えば分子量１００〜４００の脂肪酸からなる保護剤の共存下で還元処理すると、腐食性化合物の少ない粒径の揃った球状の銀の粒子粉末が得ることを知見し、特願２００５−２６８６６号明細書および図面に記載した。いずれの場合にも、その銀粒子粉末を非極性もしくは極性の小さな液状有機媒体に分散させることによって銀粒子の分散液を得ることができ、この分散液から遠心分離等で粗粒子を除くと粒径のバラツキの少ない（ＣＶ値＝標準偏差σ／個数平均粒子の百分率が４０％未満の）銀粒子が単分散した分散液を得ることができる。 The present inventor has repeatedly conducted tests for producing silver particle powder by a liquid phase method. In an alcohol having a boiling point of 85 to 150 ° C., silver nitrate is heated at a temperature of 85 to 150 ° C. (evaporated alcohol is liquid phase). For example, when a reduction treatment is performed in the presence of a protective agent composed of an amine compound having a molecular weight of 100 to 400, a spherical silver nanoparticle powder having a uniform particle size can be obtained. This is described in the specification of No. 26805 and the drawings. Further, in an alcohol or polyol having a boiling point of 85 ° C. or higher, a silver compound (typically silver carbonate or silver oxide) is mixed with a protective agent comprising a fatty acid having a molecular weight of 100 to 400, for example, at a temperature of 85 ° C. or higher. It was found that when the reduction treatment was performed, spherical silver particle powder having a uniform particle size with few corrosive compounds was obtained and described in Japanese Patent Application No. 2005-26866 and drawings. In either case, a dispersion of silver particles can be obtained by dispersing the silver particle powder in a non-polar or small polar liquid organic medium. When coarse particles are removed from the dispersion by centrifugation or the like, A dispersion in which silver particles having a small variation in diameter (CV value = standard deviation σ / percentage of number average particles is less than 40%) are monodispersed can be obtained.
しかし、これら方法では、反応温度を高くすると、液中の銀イオンが効率よく還元されるが、粒子の焼結が起こって粗粒子化し、５０ｎｍ以下の銀粒子粉末が得られ難くなり、反面、反応温度を低くすれば焼結は抑制できるが、液中の銀イオンの還元効率が低下してしまって収率が下がる等のことから、効率よく５０ｎｍ以下の銀粒子粉末の作製を行うにはさらなる改善を必要とした。 However, in these methods, when the reaction temperature is increased, the silver ions in the liquid are efficiently reduced, but the particles are sintered and coarsened, making it difficult to obtain a silver particle powder of 50 nm or less. Sintering can be suppressed by lowering the reaction temperature, but the reduction efficiency of silver ions in the solution decreases and the yield decreases. For this reason, to efficiently produce silver particle powder of 50 nm or less Further improvement was needed.
この課題に対し、有機保護剤として分子量５００以上のものを使用すると、反応温度を高くしても、焼結を抑制でき、その結果、高い還元率で５０ｎｍ以下の銀粒子粉末を高効率で得ることができることがわかった。しかし、分子量の大きい有機保護剤を用いると、その銀粒子分散液を配線形成用材料とした場合に、３００℃以下の低温での焼結性が著しく低下するという別の問題が現れることがわかった。基板に有機フィルム等を用いた回路等では、３００℃以上の温度で焼成することは実質的にできないので、該分散液の用途に制限を受けることになるし、その他の材料を用いる回路基板でも低温で焼結性がよいことは当該銀粒子分散液の価値を高めることになる。このため、高分子量の有機保護剤を用いたのでは、５０ｎｍ以下の銀粒子粉末を高収率で得ることと、その銀粒子分散液の低温焼結性とを両立させることはできない。 For this problem, when an organic protective agent having a molecular weight of 500 or more is used, sintering can be suppressed even when the reaction temperature is increased, and as a result, a silver particle powder having a high reduction rate of 50 nm or less can be obtained with high efficiency. I found out that I could do it. However, when an organic protective agent having a large molecular weight is used, another problem appears that the sinterability at a low temperature of 300 ° C. or lower remarkably deteriorates when the silver particle dispersion is used as a wiring forming material. It was. In a circuit using an organic film or the like on the substrate, firing at a temperature of 300 ° C. or more is substantially impossible, so the use of the dispersion is limited, and even a circuit substrate using other materials Good sinterability at low temperatures increases the value of the silver particle dispersion. For this reason, when a high molecular weight organic protective agent is used, it is impossible to achieve both high yield of silver particle powder of 50 nm or less and low temperature sinterability of the silver particle dispersion.
そこで、さらに研究を重ねた結果、１分子中に２重結合等の不飽和結合を１個以上持つアミン化合物を有機保護剤として用いると、前記の両立ができることを見出した。さらに、当該還元処理において、反応温度を段階的にあげて、多段反応温度で還元する処方を採用したり、得られた粒子懸濁液の洗浄および粗粒子除去の操作を高度に組み立てることによって、一層有利に前記の両立ができ、銀ナノ粒子が高度に分散した低温焼結性のよい銀粒子分散液を高収率で製造できることがわかった。 As a result of further research, it was found that the above-mentioned compatibility can be achieved by using an amine compound having at least one unsaturated bond such as a double bond in one molecule as an organic protective agent. Furthermore, in the reduction treatment, by increasing the reaction temperature step by step, adopting a formulation that reduces at a multistage reaction temperature, or by highly assembling the operations of washing the resulting particle suspension and removing coarse particles, It has been found that the above-mentioned compatibility can be achieved more advantageously, and a silver particle dispersion having a high degree of low-temperature sinterability in which silver nanoparticles are highly dispersed can be produced in a high yield.
銀以外の標準電極電位Ｅ0が０．８０Ｖ以上の金属Ｘについても、前記した銀と実質的に同様の液相法によってそのナノ金属Ｘ粒子を製造できる。その場合も、１分子中に２重結合等の不飽和結合を１個以上持つアミン化合物を有機保護剤として用いると、銀の場合と同様に、前記の両立ができる。さらに、当該還元処理において、反応温度を段階的にあげて、多段反応温度で還元する処方を採用したり、還元助剤を添加したり、得られた粒子懸濁液の洗浄および粗粒子除去の操作を高度に組み立てることによって、一層有利に前記の両立ができ、金属Ｘのナノ粒子が高度に分散した低温焼結性のよい金属粒子分散液を高収率で製造できることがわかった。 With respect to the metal X having a standard electrode potential E 0 other than silver of 0.80 V or more, the nanometal X particles can be produced by a liquid phase method substantially the same as that of silver described above. Even in that case, when an amine compound having at least one unsaturated bond such as a double bond in one molecule is used as an organic protective agent, the above-mentioned compatibility can be achieved as in the case of silver. Furthermore, in the reduction treatment, the reaction temperature is raised stepwise and a formulation that reduces at a multistage reaction temperature is adopted, a reduction aid is added, the resulting particle suspension is washed and coarse particles are removed. It has been found that the above-described compatibility can be achieved more advantageously by highly assembling the operation, and a metal particle dispersion having good low-temperature sinterability in which the metal X nanoparticles are highly dispersed can be produced in a high yield.
したがって、ナノ銀粒子とナノ金属Ｘ粒子の混合粉は、それぞれ前記の液相法で得られたものを混合することによって得ることができる。場合によっては、還元剤として機能するアルコールまたはポリオールの１種または２種以上の液中で銀イオンと金属Ｘイオンを銀粒子と金属Ｘ粒子に還元処理するさいに、１分子中に少なくとも１個以上の不飽和結合を有する分子量１００〜１０００のアミン化合物の共存下においてその還元反応の条件を制御することにより、銀粒子と金属Ｘ粒子が混合された複合金属粉体を製造することができる。またこの混合された複合金属粉体を沸点６０〜３００℃の非極性もしくは極性の小さい液状有機媒体に分散させることによって複合金属粉体の分散液を製造することができる。 Therefore, the mixed powder of nano silver particles and nano metal X particles can be obtained by mixing those obtained by the liquid phase method. In some cases, at least one per molecule when reducing silver ions and metal X ions to silver particles and metal X particles in one or more liquids of alcohol or polyol that functions as a reducing agent. A composite metal powder in which silver particles and metal X particles are mixed can be produced by controlling the conditions of the reduction reaction in the presence of an amine compound having an unsaturated bond and having a molecular weight of 100 to 1000. Further, a dispersion of the composite metal powder can be produced by dispersing the mixed composite metal powder in a non-polar or low-polar liquid organic medium having a boiling point of 60 to 300 ° C.
ナノ銀粒子に金属Ｘを複合化する第二の態様として、銀と金属Ｘとを合金化し、この合金のナノ粒子とする態様があるが、このナノ合金粒子の製造も、前記と同様の液相法で製造することができる。すなわち、還元剤として機能するアルコールまたはポリオールの１種または２種以上の液中で銀イオンと金属Ｘイオンを銀粒子と金属Ｘ粒子に還元処理するさいに、１分子中に少なくとも１個以上の不飽和結合を有する分子量１００〜１０００のアミン化合物の共存下においてその還元反応の条件を制御することにより、銀粒子と金属Ｘ粒子が合金化された複合金属粉体を製造することができる。またこの合金化された複合金属粉体を沸点６０〜３００℃の非極性もしくは極性の小さい液状有機媒体に分散させることによって合金化された複合金属粉体の分散液を製造することができる。本発明ではこの第二の態様を対象とする。 As a second aspect of compositing metal X with nano silver particles, there is an aspect in which silver and metal X are alloyed to form nanoparticles of this alloy. It can be manufactured by the phase method. That is, when reducing silver ions and metal X ions into silver particles and metal X particles in one or more liquids of alcohol or polyol that function as a reducing agent, at least one or more in one molecule. By controlling the conditions of the reduction reaction in the presence of an amine compound having an unsaturated bond and a molecular weight of 100 to 1,000, a composite metal powder in which silver particles and metal X particles are alloyed can be produced. Further, a dispersion of the alloyed composite metal powder can be produced by dispersing the alloyed composite metal powder in a non-polar or small-polar liquid organic medium having a boiling point of 60 to 300 ° C. The present invention is directed to this second aspect.
ナノ銀粒子のコアに金属Ｘのシェルを形成する（あるいはその逆の）コア−シェル構造の態様、銀粒子に金属Ｘ粒子を担持させるか金属Ｘ粒子に銀粒子を担持させる担持構造の態様においても、これらの構造のナノ粒子も前記と同様の液相法で製造できる。すなわち、還元剤として機能するアルコールまたはポリオールの１種または２種以上の液中で銀イオンと金属Ｘイオンを銀粒子と金属Ｘ粒子に還元処理するさいに、１分子中に少なくとも１個以上の不飽和結合を有する分子量１００〜１０００のアミン化合物の共存下においてその還元反応の条件を制御することにより、これらの態様の構造の複合金属粉体を製造することができる。またこの構造の複合金属粉体を沸点６０〜３００℃の非極性もしくは極性の小さい液状有機媒体に分散させることによって合金化された複合金属粉体の分散液を製造することができる。 In a core-shell structure embodiment in which a metal X shell is formed on the core of nano silver particles (or vice versa), in a support structure embodiment in which metal X particles are supported on silver particles or silver particles are supported on metal X particles In addition, nanoparticles having these structures can also be produced by the same liquid phase method as described above. That is, when reducing silver ions and metal X ions into silver particles and metal X particles in one or more liquids of alcohol or polyol that function as a reducing agent, at least one or more in one molecule. By controlling the conditions of the reduction reaction in the presence of an amine compound having an unsaturated bond and a molecular weight of 100 to 1000, a composite metal powder having the structure of these embodiments can be produced. Further, a dispersion of alloyed composite metal powder can be produced by dispersing the composite metal powder having this structure in a liquid organic medium having a boiling point of 60 to 300 ° C., which is nonpolar or small in polarity.
これらの分散液については、低温焼結性や分散性等を損なわない範囲で各種添加剤を添加することもできる。例えば増粘剤、沈降防止剤、色分かれ防止剤、消泡剤、レベリング剤等のこの分野で既知の添加材を使用することができる。それらの添加量は当該分散液の重量に対して０．０１〜１０重量％とするのが良い。０．０１重量％未満では添加剤の効果が少なく、１０重量％より多くても添加剤の効果が飽和するばかりか、低温焼結性や分散性等を悪化させるためである。 About these dispersion liquids, various additives can also be added in the range which does not impair low temperature sinterability, dispersibility, etc. For example, additives known in this field such as thickeners, anti-settling agents, anti-color separation agents, antifoaming agents, and leveling agents can be used. The addition amount thereof is preferably 0.01 to 10% by weight with respect to the weight of the dispersion. If the amount is less than 0.01% by weight, the effect of the additive is small, and if it exceeds 10% by weight, the effect of the additive is not only saturated, but also low-temperature sinterability and dispersibility are deteriorated.
また、前記いずれの態様の複合金属粉体のペーストを得るには、前記のようにして得た各態様の複合金属粉体に、分子量１０００〜１０００００の高分子有機保護剤を添加した後、沸点が６０〜３００℃の液状有機媒体に分散させるか、或いは、該複合金属粉体を沸点が６０〜３００℃の液状有機媒体に分散させた後に分子量１０００〜１０００００の高分子有機保護剤を添加することによってペースト化すればよい。高分子有機保護剤の添加は複合金属分散液の３００℃以下での低温焼結性を悪化させるが、このような高分子量の有機保護剤を用いると、分散液の粘度を高くすることができ、ペーストとして使用するのに適した粘性を付与させることができる。 Moreover, in order to obtain the composite metal powder paste of any of the above embodiments, after adding a polymer organic protective agent having a molecular weight of 1000 to 100,000 to the composite metal powder of each embodiment obtained as described above, the boiling point Is dispersed in a liquid organic medium having a molecular weight of 1000 to 100,000 after the composite metal powder is dispersed in a liquid organic medium having a boiling point of 60 to 300 ° C. It can be made into a paste. Although the addition of the polymer organic protective agent deteriorates the low temperature sintering property of the composite metal dispersion at 300 ° C. or lower, the viscosity of the dispersion can be increased by using such a high molecular weight organic protective agent. A viscosity suitable for use as a paste can be imparted.
以下に本発明で特定する事項を説明する。
〔平均粒径ＤTEM〕
本発明の複合金属粒子粉末は、ＴＥＭ（透過電子顕微鏡）観察により測定される平均粒径（ＤTEMと記す）が５０ｎｍ以下、好ましくは３０ｎｍ以下、さらに好ましくは２０ｎｍ以下である。このため、本発明の複合金属粒子粉末分散液および複合金属粒子粉末ペーストは微細な配線を形成するのに適する。ＴＥＭ観察では６０万倍に拡大した画像から重なっていない独立した粒子３００個の径を測定して平均値を求める。
The matters specified by the present invention will be described below.
[Average particle diameter D TEM ]
Composite metal particles of the present invention, TEM (referred to as D TEM) average particle size measured by (transmission electron microscope) observation 50nm or less, preferably 30nm or less, more preferably 20nm or less. For this reason, the composite metal particle powder dispersion and composite metal particle powder paste of the present invention are suitable for forming fine wiring. In TEM observation, the average value is obtained by measuring the diameter of 300 independent particles that are not overlapped from an image magnified 600,000 times.
〔Ｘ線結晶粒径Ｄｘ〕
本発明の複合金属粒子粉末は、結晶粒子径（Ｄｘと記す）が２０ｎｍ以下である。複合金属粒子粉末のＸ線結晶粒径はＸ線回折結果から Scherrer の式を用いて求めることができる。その求め方は、次のとおりである。
Scherrer の式は、次の一般式で表現される。
Ｄｘ＝Ｋ・λ／β COSθ
式中、Ｋ：Scherrer定数、Ｄｘ：結晶粒子径、λ：測定Ｘ線波長、β：Ｘ線回折で得られたピークの半価幅、θ：回折線のブラッグ角をそれぞれ表す。Ｋは０．９４の値を採用し、Ｘ線の管球はＣｕを用いると、前式は下式のように書き換えられる。
Ｄｘ＝0.94×1.5405／β COSθ
[X-ray crystal grain size Dx]
The composite metal particle powder of the present invention has a crystal particle diameter (denoted as Dx) of 20 nm or less. The X-ray crystal grain size of the composite metal particle powder can be determined from the X-ray diffraction result using the Scherrer equation. How to find it is as follows.
Scherrer's formula is expressed by the following general formula.
Dx = K · λ / β COSθ
In the formula, K: Scherrer constant, Dx: crystal particle diameter, λ: measured X-ray wavelength, β: half width of peak obtained by X-ray diffraction, θ: Bragg angle of diffraction line. If K adopts a value of 0.94 and the X-ray tube uses Cu, the previous equation can be rewritten as the following equation.
Dx = 0.94 × 1.5405 / β COSθ
〔標準電極電位Ｅ0が０．８０Ｖ以上の金属Ｘ〕
標準電極電位Ｅ0が０．８０Ｖ以上の銀以外の金属Ｘとして、白金（標準電極電位Ｅ0＝１．１９Ｖ）、パラジウム（標準電極電位Ｅ0＝０．９１５Ｖ）、金（標準電極電位Ｅ0＝１．６８Ｖ）等を例示できるが、これらの金属Ｘは焼成時に銀と合金を形成することにより耐エレクトロマイグレーション性を改善し、また耐めっき性、耐半田喰われ性を向上させる。配線部や電気的接点での合金組成は部分的な斑がないことが好ましく、混合態様の本発明の複合金属粉体でもこれらの効果を示す。しかし、予め合金化もしくはコア−シェル構造もしくは担持構造を形成させた態様の方が、耐エレクトロマイグレーション性や耐めっき性や耐半田喰われ性を一層確実なものとすることができる。なお、金属Ｘの出発原料や還元剤等に硫黄や塩素を含むものは、生成した金属粉体に硫黄や塩素が残存し、配線腐食の原因となるので好ましくない。
[Metal X with standard electrode potential E 0 of 0.80V or more]
As the standard electrode potential E 0 is metal X except more silver 0.80 V, platinum (standard electrode potential E 0 = 1.19V), palladium (standard electrode potential E 0 = 0.915V), gold (standard electrode potential E 0 = 1.68V) and the like, but these metals X improve the electromigration resistance by forming an alloy with silver at the time of firing, and also improve the plating resistance and solder erosion resistance. It is preferable that the alloy composition in the wiring part and the electrical contact is free from partial spots, and the mixed metal powder of the present invention in the mixed mode also exhibits these effects. However, the aspect in which the alloying, the core-shell structure, or the supporting structure is formed in advance can further ensure the electromigration resistance, the plating resistance, and the solder erosion resistance. It is not preferable that the starting material for metal X, the reducing agent, etc. contain sulfur or chlorine, since sulfur or chlorine remains in the generated metal powder, causing wiring corrosion.
〔有機保護剤〕
本発明においては、表面が有機保護剤で覆われた複合金属粉体を液状有機媒体に分散させることによって複合金属粉体の分散液とする。この有機保護剤としては、１分子中に少なくとも１個以上の不飽和結合を有し、分子量１００〜１０００、好ましくは１００〜４００のアミン化合物を使用する。このような不飽和結合をもつアミン化合物を有機保護剤として使用することによって、液相法による還元反応において金属核を一斉に発生させると共に析出した金属核の成長を全体的に均斉に抑制する現象が起きるのではないかと推測されるが、前記のように２０ｎｍ以下の金属粒子粉末を高収率で得ることができ、しかもこのアミン化合物は比較的低温で分解するのでその金属粒子分散液の低温焼結性を確保することができる。本発明で使用できる代表的なアミン化合物として、例えばトリアリルアミン、オレイルアミン、ジオレイルアミン、オレイルプロピレンジアミンを例示できる。なお、有機保護剤に硫黄や塩素を含むものは配線腐食の原因となるので好ましくない。
[Organic protective agent]
In the present invention, a composite metal powder having a surface covered with an organic protective agent is dispersed in a liquid organic medium to obtain a composite metal powder dispersion. As the organic protective agent, an amine compound having at least one unsaturated bond in one molecule and having a molecular weight of 100 to 1000, preferably 100 to 400 is used. Phenomenon that suppresses the growth of precipitated metal nuclei as a whole by generating metal nuclei simultaneously in the reduction reaction by the liquid phase method by using such an amine compound having an unsaturated bond as an organic protective agent. As described above, it is possible to obtain a metal particle powder of 20 nm or less in a high yield, and this amine compound decomposes at a relatively low temperature, so that the low temperature of the metal particle dispersion is low. Sinterability can be ensured. Examples of typical amine compounds that can be used in the present invention include triallylamine, oleylamine, dioleylamine, and oleylpropylenediamine. An organic protective agent containing sulfur or chlorine is not preferable because it causes wiring corrosion.
〔高分子量有機保護剤〕
高分子量の有機保護剤を用いると、銀粒子分散液の粘度を高くすることができ、ペーストとして使用するのに適した粘性を付与させることができる。高分子量の有機保護剤は分子量１０００〜１０００００の有機化合物を使用する。本発明で使用できる代表的な有機化合物として、例えばエポキシ樹脂、ウレタン樹脂、シリコーン樹脂、アクリル樹脂、ポリエステル樹脂、エチルセルロース樹脂、ポリビニルピロリドン樹脂、ポリビニルアルコール樹脂、ヒドロキシプロプルメチルセルロースフタレート樹脂等のポリマーや脂肪族系多価カルボン酸、高分子ポリエステルのアミン塩、長鎖ポリアミノアマイドと高分子酸ポリエステルの塩、特殊アクリル系重合物、特殊シリコーン系重合物等の界面活性剤を例示できる。なお、高分子量有機保護剤に硫黄や塩素を含むものは配線腐食の原因となるので好ましくない。
[High molecular weight organic protective agent]
When a high molecular weight organic protective agent is used, the viscosity of the silver particle dispersion can be increased, and a viscosity suitable for use as a paste can be imparted. As the high molecular weight organic protective agent, an organic compound having a molecular weight of 1,000 to 100,000 is used. Examples of typical organic compounds that can be used in the present invention include polymers such as epoxy resins, urethane resins, silicone resins, acrylic resins, polyester resins, ethyl cellulose resins, polyvinyl pyrrolidone resins, polyvinyl alcohol resins, hydroxypropyl methyl cellulose phthalate resins, and fats. Examples include surfactants such as aliphatic polycarboxylic acids, amine salts of high molecular polyesters, salts of long-chain polyaminoamides and high molecular acid polyesters, special acrylic polymers, and special silicone polymers. A high molecular weight organic protective agent containing sulfur or chlorine is not preferable because it causes wiring corrosion.
〔液状有機媒体〕
前記の有機保護剤で覆われた複合金属粉体を分散させる液状有機媒体としては、沸点が６０〜３００℃の非極性もしくは極性の小さい液状有機媒体を用いる。ここで、「非極性もしくは極性の小さい」というのは２５℃での比誘電率が１５以下であることを指し、より好ましく５以下である。比誘電率が１５を超える場合、複合金属粉体の分散性が悪化し沈降することがあり、好ましくない。分散液の用途に応じて各種の液状有機媒体が使用できるが、炭化水素系が好適に使用でき、とくに、イソオクタン、ｎ−デカン、イソドデカン、イソヘキサン、ｎ−ウンデカン、ｎ−テトラデカン、ｎ−ドデカン、トリデカン、ヘキサン、ヘプタン等の脂肪族炭化水素、ベンゼン、トルエン、キシレン、エチルベンゼン、デカリン、テトラリン等の芳香族炭化水素等が使用できる。これらの液状有機媒体は１種類または２種類以上を使用することができ、ケロシンのような混合物であっても良い。更に、極性を調整するために、混合後の液状有機媒体の２５℃での比誘電率が１５以下となる範囲でアルコール系、ケトン系、エーテル系、エステル系等の極性有機媒体を添加しても良い。
[Liquid organic medium]
As the liquid organic medium in which the composite metal powder covered with the organic protective agent is dispersed, a nonpolar or small polarity liquid organic medium having a boiling point of 60 to 300 ° C. is used. Here, “non-polar or low polarity” means that the relative dielectric constant at 25 ° C. is 15 or less, more preferably 5 or less. When the relative dielectric constant exceeds 15, the dispersibility of the composite metal powder may deteriorate and settle, which is not preferable. Various liquid organic media can be used depending on the use of the dispersion, but hydrocarbons can be preferably used. In particular, isooctane, n-decane, isododecane, isohexane, n-undecane, n-tetradecane, n-dodecane, Aliphatic hydrocarbons such as tridecane, hexane and heptane, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, decalin and tetralin can be used. These liquid organic media may be used alone or in combination of two or more, and may be a mixture such as kerosene. Further, in order to adjust the polarity, polar organic media such as alcohols, ketones, ethers, esters, etc. are added within a range where the relative permittivity at 25 ° C. of the mixed liquid organic media is 15 or less. Also good.
〔アルコールまたはポリオール〕
本発明では還元剤として機能するアルコールまたはポリオールの１種または２種以上の液中で銀や金属Ｘの化合物（銀イオンや金属Ｘイオン）を還元するが、このようなアルコールとしては、プロピルアルコール、イソプロピルアルコール、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール、アリルアルコール、クロチルアルコール、シクロペンタノール等が使用できる。またポリオールとしては、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール等が使用できる。
[Alcohol or polyol]
In the present invention, a compound of silver or metal X (silver ion or metal X ion) is reduced in one or more liquids of alcohol or polyol that functions as a reducing agent. Such alcohol includes propyl alcohol. Isopropyl alcohol, n-butanol, isobutanol, sec-butyl alcohol, tert-butyl alcohol, allyl alcohol, crotyl alcohol, cyclopentanol and the like can be used. As the polyol, diethylene glycol, triethylene glycol, tetraethylene glycol, or the like can be used.
〔還元反応〕
本発明の複合金属粉体は、アルコールまたはポリオール中で、銀もしくは金属Ｘの化合物（各種の金属塩や銀酸化物等）を、有機保護剤の共存下で、８５℃〜１５０℃の温度で還元処理することによって製造することができる。有機保護剤としては前記のとおり１分子中に１個以上の不飽和結合を有する分子量１００〜１０００のアミン化合物を使用する。アルコールまたはポリオールは、銀もしくは金属Ｘの化合物の還元剤として、また反応系の液状有機媒体として機能するものである。還元反応は加熱下でこの液状有機媒体兼還元剤の蒸発と凝縮を繰り返す還流条件下で行なわせるのがよい。還元に供する銀もしくは金属Ｘの化合物としては、銀もしくは金属Ｘの酸化物、硝酸塩、炭酸塩、脂肪酸塩等がある。工業的観点から硝酸塩が好ましいが、硝酸塩に限定されるものではない。ただし、出発原料である銀もしくは金属Ｘの化合物（各種の金属塩や銀酸化物等）に硫黄や塩素を含むものは配線腐食の原因となるので好ましくない。本発明法では反応時の液中の銀もしくは金属Ｘのイオン濃度は５０ｍｍｏｌ／Ｌ以上で行うことができる。還元処理にあたっては、反応温度を段階的にあげて、多段反応温度で還元処理する方法も有利である。
[Reduction reaction]
The composite metal powder of the present invention is a compound of silver or metal X (various metal salts, silver oxides, etc.) in alcohol or polyol at a temperature of 85 ° C. to 150 ° C. in the presence of an organic protective agent. It can manufacture by carrying out a reduction process. As described above, an amine compound having a molecular weight of 100 to 1000 and having one or more unsaturated bonds in one molecule is used as the organic protective agent. The alcohol or polyol functions as a reducing agent for the silver or metal X compound and as a liquid organic medium for the reaction system. The reduction reaction is preferably performed under reflux conditions in which the liquid organic medium / reducing agent is repeatedly evaporated and condensed under heating. Examples of silver or metal X compounds to be used for reduction include silver or metal X oxides, nitrates, carbonates and fatty acid salts. Although nitrate is preferable from an industrial viewpoint, it is not limited to nitrate. However, silver or metal X compounds (various metal salts, silver oxides, etc.) containing sulfur or chlorine as starting materials are not preferable because they cause wiring corrosion. In the method of the present invention, the ion concentration of silver or metal X in the solution during the reaction can be performed at 50 mmol / L or more. In the reduction treatment, a method of raising the reaction temperature stepwise and carrying out reduction treatment at a multistage reaction temperature is also advantageous.
この還元反応において、反応温度、昇温速度、反応物の仕込量や量比、還元助剤の添加、その他の還元反応を律速する因子をコントロールしたり、出発原料種類を選択することにより、銀と金属Ｘとの複合金属粉体の形態制御、すなわち混合物形態、コア−シェル構造形態、担持形態等の態様のものを得ることができる。 In this reduction reaction, by controlling the reaction temperature, the rate of temperature rise, the amount and ratio of reactants added, the addition of a reduction aid, other factors that limit the reduction reaction, or by selecting the starting material type, It is possible to obtain the form control of the composite metal powder of the metal X and the metal X, that is, the mixture form, the core-shell structure form, the support form and the like.
〔反応後の処理〕
反応後の銀もしくは金属Ｘ、または複合金属粉体の懸濁液（反応直後のスラリー）は、洗浄・分散・分級・混合等の工程を経て、本発明に従う複合金属粉体の分散液とすることができるが、それら工程の代表例（後記の実施例で用いた例）を挙げると次のとおりである。
[Processing after reaction]
The silver or metal X after the reaction or the suspension of the composite metal powder (slurry immediately after the reaction) is subjected to washing, dispersion, classification, mixing, and the like to obtain a dispersion of the composite metal powder according to the present invention. However, typical examples of these steps (examples used in the examples described later) are as follows.
〔洗浄工程〕
(1) 反応後のスラリー４０ｍＬを遠心分離器（日立工機株式会社製のＣＦ７Ｄ２）を用いて３０００ｒｐｍで３０分固液分離を実施し、上澄みを廃棄する。
(2) 沈殿物に「極性の大きい液状有機媒体」４０ｍＬを加えて超音波分散機で分散させる。
(3) 前記の(1) →(2) を３回繰り返す。
(4) 前記の(1) を実施して上澄み廃棄し沈殿物を得る。
[Washing process]
(1) 40 mL of the slurry after the reaction is subjected to solid-liquid separation at 3000 rpm for 30 minutes using a centrifuge (CF7D2 manufactured by Hitachi Koki Co., Ltd.), and the supernatant is discarded.
(2) Add 40 mL of “polar organic liquid medium having a large polarity” to the precipitate and disperse with an ultrasonic disperser.
(3) Repeat (1) → (2) three times.
(4) Carry out the above (1) and discard the supernatant to obtain a precipitate.
〔分散工程〕
(1) 前記の洗浄工程を得た沈殿物に「非極性もしくは極性の小さい液状有機媒体」４０ｍＬ添加する。
(2) 次いで超音波分散機にかける。
[Dispersing process]
(1) Add 40 mL of “non-polar or low-polar liquid organic medium” to the precipitate obtained in the washing step.
(2) Then apply to an ultrasonic disperser.
〔分級工程〕
(1) 分散工程を経た銀もしくは金属Ｘもしくは複合金属粒子と「非極性もしくは極性の小さい液状有機媒体の混濁液」４０ｍＬを前記と同様の遠心分離器を用いて３０００ｒｐｍで３０分間固液分離を実施する。
(2) 上澄み液を回収する。この上澄み液が銀もしくは金属Ｘもしくは複合金属粒子粉末分散液となる。
[Classification process]
(1) Silver / metal X or composite metal particles that have undergone the dispersion process and 40 mL of “a turbid liquid of a nonpolar or small polar liquid organic medium” are subjected to solid-liquid separation at 3000 rpm for 30 minutes using a centrifuge similar to the above. carry out.
(2) Collect the supernatant. This supernatant becomes silver, metal X, or composite metal particle powder dispersion.
前記の洗浄工程では液状有機媒体としては「極性の大きい液状有機媒体」を用いる。「極性の大きい」というのは２５℃での比誘電率が１５より大きいことを指す。比誘電率が１５以下の場合、銀もしくは金属Ｘもしくは複合金属粒子の分散性が良好すぎるため、洗浄工程での洗浄効率が悪化する。極性の大きい液状有機媒体としては各種のものが使用できるが、アルコール系とケトン系が好適に使用でき、アルコール系としては、とくに、メタノール、エタノール、プロピルアルコール、イソプロピルアルコール等が、ケトン系としてはアセトン、アセチルアセトン等が使用できる。これらの極性の大きい液状有機媒体は１種類または２種類以上を使用することができ、混合物であっても良い。 In the washing step, a “liquid organic medium having a large polarity” is used as the liquid organic medium. “Large polarity” means that the relative dielectric constant at 25 ° C. is larger than 15. When the relative dielectric constant is 15 or less, the dispersibility of silver, metal X, or composite metal particles is too good, so that the cleaning efficiency in the cleaning step is deteriorated. Various types of liquid organic media having a large polarity can be used, but alcohols and ketones can be preferably used. As alcohols, methanol, ethanol, propyl alcohol, isopropyl alcohol, etc. are particularly preferred as ketones. Acetone, acetylacetone, etc. can be used. These liquid organic media having a large polarity can be used alone or in combination of two or more, and may be a mixture.
また、次の分散工程では「非極性もしくは極性の小さい液状有機媒体」を用いる。「非極性もしくは極性の小さい」というのは、既に説明したとおり、２５℃での比誘電率が１５以下であることを指し、より好ましく５以下であって、前掲例示の非極性もしくは極性の小さい液状有機媒体を使用することができる。 In the next dispersion step, a “nonpolar or small polarity liquid organic medium” is used. “Nonpolar or low polarity” means that the relative dielectric constant at 25 ° C. is 15 or less as described above, more preferably 5 or less, and the nonpolarity or low polarity exemplified above. Liquid organic media can be used.
〔耐マイグレーション性〕
耐マイグレーション性は次のようにして評価する。本発明による複合金属粒子分散液もしくは複合金属粒子分散ペーストをアルミナ基板上に塗布し、大気雰囲気中２５０℃で６０分焼成し、電極幅１ｍｍ、電極間距離１ｍｍの電極を作製し、７．５Ｖの直流電圧を印加した電極の間に純水を１滴滴下してから、抵抗の両端電圧が２Ｖになるまでの時間を測定する。この時間をマイグレーション時間とする。
[Migration resistance]
The migration resistance is evaluated as follows. The composite metal particle dispersion or composite metal particle dispersion paste according to the present invention is applied onto an alumina substrate and baked at 250 ° C. for 60 minutes in an air atmosphere to produce an electrode having an electrode width of 1 mm and an interelectrode distance of 1 mm. After a drop of pure water is dropped between the electrodes to which the direct current voltage is applied, the time until the voltage across the resistor reaches 2 V is measured. This time is set as the migration time.
〔耐半田喰われ性〕
耐半田喰われ性は次のようにして評価する。本発明による複合金属粉体分散液もしくは複合金属粉体ペーストをアルミナ基板上に塗布し、大気雰囲気中２５０℃で６０分焼成し、２ｍｍ角の電極を作製する。電極をフラックスに２秒浸漬し引き上げた後、過剰なフラックスを除去し、２３０℃の半田槽に５秒間浸漬し引き上げる。表面をアセトンで洗浄してから半田喰われを目視により確認する。
[Solder erosion resistance]
Solder erosion resistance is evaluated as follows. The composite metal powder dispersion or the composite metal powder paste according to the present invention is applied onto an alumina substrate and fired at 250 ° C. for 60 minutes in an air atmosphere to produce a 2 mm square electrode. After the electrode is dipped in the flux for 2 seconds and then pulled up, the excess flux is removed, and dipped in a solder bath at 230 ° C. for 5 seconds and pulled up. After the surface is washed with acetone, the solder bite is visually confirmed.
〔本発明の複合金属粉体の用途〕
本発明の複合金属粉体は、微細な回路パターンを形成するための配線形成用材料例えばインクジェット法による配線形成用材料として好適である。また本発明の複合金属粉体はＬＳＩ基板の配線やＦＰＤ（フラットパネルディスプレイ）の電極、配線用途、さらには微細なトレンチ、ビアホール、コンタクトホールの埋め込み等の配線形成材料としても好適である。さらに本発明の複合金属粉体は車の塗装等の色材としても適用でき、医療・診断・バイオテクノロジー分野において生化学物質等を吸着させるキャリヤーにも適用できる。さらに本発明の複合金属粉体は低温焼成が可能であるからフレキシブルなフィルム上への電極形成材料として適用でき、エレクトロニクス実装に於いては接合材として用いることも出来る。さらには、導電性皮膜として電磁波シールド膜や、透明導電膜等の分野での光学特性を利用した赤外線反射シールド等にも適用できる。さらに、低温焼結性と導電性を利用して、ガラス基板上へ印刷・焼成し、自動車ウインドウの防曇用熱線等にも好適である。一方、分散液としては、液体（分散媒）とほぼ同様の挙動を示すため、上に挙げたインクジェット法に限らず、スピンコート、ディッピング、ブレードコート等各種塗布方法に適用可能で、スクリーン印刷等にも適用可能である。
[Use of the composite metal powder of the present invention]
The composite metal powder of the present invention is suitable as a wiring forming material for forming a fine circuit pattern, for example, a wiring forming material by an ink jet method. The composite metal powder of the present invention is also suitable as a wiring forming material for LSI substrate wiring, FPD (flat panel display) electrodes, wiring applications, and for embedding fine trenches, via holes, and contact holes. Furthermore, the composite metal powder of the present invention can be applied as a coloring material for car paints and the like, and can also be applied to a carrier that adsorbs biochemical substances and the like in the medical, diagnostic, and biotechnology fields. Furthermore, since the composite metal powder of the present invention can be fired at a low temperature, it can be applied as an electrode forming material on a flexible film, and can also be used as a bonding material in electronic packaging. Further, the present invention can be applied to an electromagnetic wave shielding film as a conductive film, an infrared reflection shield using optical characteristics in the field of a transparent conductive film, and the like. Furthermore, using low-temperature sintering and electrical conductivity, printing and baking on a glass substrate is suitable for antifogging heat rays for automobile windows. On the other hand, since the dispersion exhibits almost the same behavior as the liquid (dispersion medium), it is applicable not only to the above-described ink jet method but also to various coating methods such as spin coating, dipping, blade coating, screen printing, etc. It is also applicable to.
〔参考例１〕
液媒体兼還元剤としてのイソブタノール１４０ｍＬに、有機保護剤として不飽和結合を分子中に１個有するオレイルアミン１８５．８ｍＬと、銀化合物として硝酸銀結晶１９．２ｇとを添加し、マグネットスターラーにて攪拌して硝酸銀を分散させる。この液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該液をマグネットスターラーにより１００ｒｐｍの回転速度で撹拌しつつ加熱し、１００℃の温度で２時間３０分の還流を行った。その後、１０８℃まで温度を上げ、２時間３０分の還流を行い、反応を終了した。そのさい１００℃および１０８℃に至るまでの昇温速度はいずれも２℃／ｍｉｎとした。
[ Reference Example 1]
Add 185.8 mL of oleylamine having one unsaturated bond in the molecule as an organic protective agent and 19.2 g of silver nitrate crystals as a silver compound to 140 mL of isobutanol as a liquid medium and reducing agent, and stir with a magnetic stirrer. To disperse the silver nitrate. This liquid is transferred to a container equipped with a reflux device and placed in an oil bath, and the liquid is stirred at a rotational speed of 100 rpm by a magnetic stirrer while blowing nitrogen gas as an inert gas at a flow rate of 400 mL / min. The mixture was heated and refluxed at a temperature of 100 ° C. for 2 hours and 30 minutes. Thereafter, the temperature was raised to 108 ° C., refluxing was performed for 2 hours and 30 minutes, and the reaction was completed. At that time, the heating rate up to 100 ° C. and 108 ° C. was set to 2 ° C./min.
反応終了後のスラリーについて本文に記載した洗浄、分散および分級の工程を実施し、本文に記載した方法で諸特性の評価を行なった。液状有機媒体として、洗浄工程では極性の大きいメタノールを、分散工程では極性の小さいケロシンを使用した。その結果、得られた銀粒子粉末は平均粒径ＤTEM＝１２．３ｎｍで、結晶粒子径Ｄｘ＝１５．０ｎｍであった。 The slurry after the reaction was subjected to the washing, dispersing and classification steps described in the text, and various properties were evaluated by the methods described in the text. As the liquid organic medium, methanol having a high polarity was used in the washing step, and kerosene having a low polarity was used in the dispersion step. As a result, the obtained silver particle powder had an average particle diameter D TEM = 12.3 nm and a crystal particle diameter Dx = 15.0 nm.
液媒体兼還元剤としてのイソブタノール２００ｍＬに、有機保護剤としてオレイルアミンを１３２．７ｍＬと、白金化合物としてのアセチルアセトナート白金を１５．９ｇ添加し、マグネットスターラーにて攪拌してアセチルアセトナート白金を分散させる。この液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該液をマグネットスターラーにより２００ｒｐｍの回転速度で撹拌しつつ加熱し、１００℃の温度で1 時間３０分の還流を行った。その後、１０８℃まで温度を上げ、２時間３０分の還流を行い、反応を終了した。そのさい１００℃および１０８℃に至るまでの昇温速度はいずれも２℃／ｍｉｎとした。 Add 132.7 mL of oleylamine as an organic protective agent and 15.9 g of acetylacetonate platinum as a platinum compound to 200 mL of isobutanol as a liquid medium and reducing agent, and stir with a magnetic stirrer to add acetylacetonate platinum. Disperse. This liquid is transferred to a container equipped with a reflux device and placed in an oil bath, and the liquid is stirred at a rotational speed of 200 rpm by a magnetic stirrer while blowing nitrogen gas as an inert gas at a flow rate of 400 mL / min. The mixture was heated and refluxed at a temperature of 100 ° C. for 1 hour and 30 minutes. Thereafter, the temperature was raised to 108 ° C., refluxing was performed for 2 hours and 30 minutes, and the reaction was completed. At that time, the heating rate up to 100 ° C. and 108 ° C. was set to 2 ° C./min.
反応終了後のスラリーについて本文に記載した洗浄、分散および分級の工程を実施し、本文に記載した方法で諸特性の評価を行なった。液状有機媒体として、洗浄工程では極性の大きいメタノールを、分散工程では極性の小さいケロシンを使用した。その結果、得られた白金粒子は平均粒径ＤTEM＝９．０ｎｍで結晶粒子径Ｄｘ＝７．８ｎｍであった。 The slurry after the reaction was subjected to the washing, dispersing and classification steps described in the text, and various properties were evaluated by the methods described in the text. As the liquid organic medium, methanol having a high polarity was used in the washing step, and kerosene having a low polarity was used in the dispersion step. As a result, the obtained platinum particles had an average particle diameter D TEM = 9.0 nm and a crystal particle diameter Dx = 7.8 nm.
前記方法で得られた銀粒子分散液と、前記方法で得られた白金粒子分散液とを混合し、複合金属粉体および複合金属粉体分散液を得た。混合にあたっては、銀粒子分散液と白金粒子分散液を、複合金属粉体中の白金粒子粉末の重量割合が４０wt％となるように分取し、マグネットスターラーにより１００ｒｐｍの回転速度で室温において撹拌混合した。 The silver particle dispersion obtained by the above method and the platinum particle dispersion obtained by the above method were mixed to obtain a composite metal powder and a composite metal powder dispersion. In mixing, the silver particle dispersion and the platinum particle dispersion are separated so that the weight ratio of the platinum particle powder in the composite metal powder is 40 wt%, and stirred and mixed at room temperature with a magnetic stirrer at a rotation speed of 100 rpm. did.
得られた複合金属粉体は銀粒子粉末と白金粒子粉末の混合物であり、複合金属粉体中の銀粒子粉末の平均粒径ＤTEM＝１２．３ｎｍで結晶粒子径Ｄｘ＝１５．０ｎｍであり、白金粒子粉末の平均粒径ＤTEM＝９．０ｎｍで結晶粒子径Ｄｘ＝７．８ｎｍであって、複合金属粉体中の白金粒子粉末の重量割合が４０wt％であった。この混合物からなる複合金属粉体について、本文に記載した方法で特性の評価を行った。その結果、エレクトロマイグレーション時間は５秒であり、耐半田喰われ性が良好であることが目視で確認された。 The obtained composite metal powder is a mixture of silver particle powder and platinum particle powder, and the average particle diameter D TEM = 12.3 nm of the silver particle powder in the composite metal powder and the crystal particle diameter Dx = 15.0 nm. The average particle diameter D TEM of the platinum particle powder was 9.0 nm, the crystal particle diameter was Dx = 7.8 nm, and the weight ratio of the platinum particle powder in the composite metal powder was 40 wt%. The composite metal powder composed of this mixture was evaluated for characteristics by the method described in the text. As a result, the electromigration time was 5 seconds, and it was visually confirmed that the solder erosion resistance was good.
〔実施例１〕
液媒体兼還元剤としてのイソブタノール１４０ｍＬに、有機保護剤として不飽和結合を分子中に１個有するオレイルアミン１８５．８ｍＬと、銀化合物として硝酸銀結晶１９．２ｇと、パラジウム化合物として硝酸パラジウム結晶１１．２ｇとを添加し、マグネットスターラーにて攪拌して硝酸銀と硝酸パラジウム分散させる。この液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該液をマグネットスターラーにより１００ｒｐｍの回転速度で撹拌しつつ加熱し、１００℃の温度で２時間３０分の還流を行った。その後、１１０℃まで温度を上げ４時間の還流を行い、反応を終了した。そのさい１００℃および１１０℃に至るまでの昇温速度はいずれも２℃／ｍｉｎとした。
[Example 1 ]
140 mL of isobutanol as a liquid medium and reducing agent, 185.8 mL of oleylamine having one unsaturated bond in the molecule as an organic protective agent, 19.2 g of silver nitrate crystals as a silver compound, and palladium nitrate crystals as a palladium compound. 2 g is added and stirred with a magnetic stirrer to disperse silver nitrate and palladium nitrate. This liquid is transferred to a container equipped with a reflux device and placed in an oil bath, and the liquid is stirred at a rotational speed of 100 rpm by a magnetic stirrer while blowing nitrogen gas as an inert gas at a flow rate of 400 mL / min. The mixture was heated and refluxed at a temperature of 100 ° C. for 2 hours and 30 minutes. Thereafter, the temperature was raised to 110 ° C. and refluxed for 4 hours to complete the reaction. At that time, the rate of temperature increase until reaching 100 ° C. and 110 ° C. was 2 ° C./min.
反応終了後のスラリーについて本文に記載した洗浄、分散および分級の工程を実施し、本文に記載した方法で諸特性の評価を行なった。液状有機媒体として、洗浄工程では極性の大きいメタノールを、分散工程では極性の小さいケロシンを使用した。その結果、得られた複合金属粉体は、パラジウム含有量が３０重量％で銀含有量が７０重量％の銀−パラジウム合金の粒子からなり、この合金粒子は平均粒径ＤTEM＝９．５ｎｍで結晶粒子径Ｄｘ＝８．９ｎｍであった。この複合金属粉体を本文に記載した方法で特性評価を行ったところ、エレクトロマイグレーション時間は８秒であり、耐半田喰われ性が良好であることが目視で確認された。 The slurry after the reaction was subjected to the washing, dispersing and classification steps described in the text, and various properties were evaluated by the methods described in the text. As the liquid organic medium, methanol having a high polarity was used in the washing step, and kerosene having a low polarity was used in the dispersion step. As a result, the obtained composite metal powder was composed of particles of a silver-palladium alloy having a palladium content of 30% by weight and a silver content of 70% by weight. The alloy particles had an average particle diameter D TEM = 9.5 nm. The crystal particle diameter Dx was 8.9 nm. When this composite metal powder was characterized by the method described in the text, the electromigration time was 8 seconds, and it was confirmed visually that the solder erosion resistance was good.
〔参考例２〕
液媒体兼還元剤としてのイソブタノール１４０ｍＬに、有機保護剤として不飽和結合を分子中に１個有するオレイルアミン１８５．８ｍＬと、銀化合物として酸化銀１９．２ｇと、パラジウム化合物として硝酸パラジウム結晶１．４ｇとを添加し、マグネットスターラーにて攪拌して酸化銀と硝酸パラジウムを分散させる。この液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該液をマグネットスターラーにより２００ｒｐｍの回転速度で撹拌しつつ加熱し、１００℃の温度で２時間３０分の還流を行った。その後、１０８℃まで温度を上げ、２時間３０分の還流を行い、反応を終了した。そのさい１００℃および１０８℃に至るまでの昇温速度はいずれも２℃／ｍｉｎとした。
[ Reference Example 2 ]
140 mL of isobutanol as a liquid medium and reducing agent, 185.8 mL of oleylamine having one unsaturated bond in the molecule as an organic protective agent, 19.2 g of silver oxide as a silver compound, and palladium nitrate crystals as a palladium compound. 4 g is added and stirred with a magnetic stirrer to disperse silver oxide and palladium nitrate. This liquid is transferred to a container equipped with a reflux device and placed in an oil bath, and the liquid is stirred at a rotational speed of 200 rpm by a magnetic stirrer while blowing nitrogen gas as an inert gas at a flow rate of 400 mL / min. The mixture was heated and refluxed at a temperature of 100 ° C. for 2 hours and 30 minutes. Thereafter, the temperature was raised to 108 ° C., refluxing was performed for 2 hours and 30 minutes, and the reaction was completed. At that time, the heating rate up to 100 ° C. and 108 ° C. was set to 2 ° C./min.
反応終了後のスラリーについて本文に記載した洗浄、分散および分級の工程を実施し、本文に記載した方法で諸特性の評価を行なった。液状有機媒体として、洗浄工程では極性の大きいメタノールを、分散工程では極性の小さいケロシンを使用した。その結果、得られた複合金属粉体は、パラジウムをコアとし、銀をシェルとしたコア−シェル構造のものであり、平均粒径ＤTEM＝６．７ｎｍであった。 The slurry after the reaction was subjected to the washing, dispersing and classification steps described in the text, and various properties were evaluated by the methods described in the text. As the liquid organic medium, methanol having a high polarity was used in the washing step, and kerosene having a low polarity was used in the dispersion step. As a result, the obtained composite metal powder had a core-shell structure with palladium as a core and silver as a shell, and had an average particle diameter D TEM = 6.7 nm.
液媒体兼還元剤としてのイソブタノール２００ｍＬに、有機保護剤としてオレイルアミンを１３２．７ｍＬと、白金化合物としてのアセチルアセトナート白金（白金の標準電極電位Ｅ0＝１．１９Ｖ）を１５．９ｇ添加し、マグネットスターラーにて攪拌してアセチルアセトナート白金を分散させる。この液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該液をマグネットスターラーにより２００ｒｐｍの回転速度で撹拌しつつ加熱し、１００℃の温度で1 時間３０分の還流を行った。その後、１０８℃まで温度を上げ、２時間３０分の還流を行い、反応を終了した。そのさい１００℃および１０８℃に至るまでの昇温速度はいずれも２℃／ｍｉｎとした。 To 200 mL of isobutanol as a liquid medium and reducing agent, 132.7 mL of oleylamine as an organic protecting agent and 15.9 g of acetylacetonate platinum (platinum standard electrode potential E 0 = 1.19 V) as a platinum compound were added. Then, stir with a magnetic stirrer to disperse the acetylacetonate platinum. This liquid is transferred to a container equipped with a reflux device and placed in an oil bath, and the liquid is stirred at a rotational speed of 200 rpm by a magnetic stirrer while blowing nitrogen gas as an inert gas at a flow rate of 400 mL / min. The mixture was heated and refluxed at a temperature of 100 ° C. for 1 hour and 30 minutes. Thereafter, the temperature was raised to 108 ° C., refluxing was performed for 2 hours and 30 minutes, and the reaction was completed. At that time, the heating rate up to 100 ° C. and 108 ° C. was set to 2 ° C./min.
反応終了後のスラリーについて本文に記載した洗浄、分散および分級の工程を実施し、本文に記載した方法で諸特性の評価を行なった。液状有機媒体として、洗浄工程では極性の大きいメタノールを、分散工程では極性の小さいケロシンを使用した。その結果、得られた白金粒子粉末は、平均粒径ＤTEM＝９．０ｎｍ、結晶粒子径Ｄｘ＝７．８ｎｍであった。 The slurry after the reaction was subjected to the washing, dispersing and classification steps described in the text, and various properties were evaluated by the methods described in the text. As the liquid organic medium, methanol having a high polarity was used in the washing step, and kerosene having a low polarity was used in the dispersion step. As a result, the obtained platinum particle powder had an average particle diameter D TEM = 9.0 nm and a crystal particle diameter Dx = 7.8 nm.
前記方法で得られたパラジウムをコア、銀をシェルとしたコア−シェル構造の複合金属粉体分散液と、前記方法で得られた白金粒子分散液とを混合することにより該コア−シェル構造の複合金属粒子粉末と白金粉末粒子とが混合された複合金属粉体および複合金属粉体分散液を得た。混合にあたっては、パラジウムをコア、銀をシェルとしたコア−シェル構造の複合金属粉体分散液と白金粉末分散液とを、パラジウム：銀：白金の重量割合が３：５７：４０となるように分取し、マグネットスターラーによりにより１００ｒｐｍの回転速度で室温において撹拌混合した。 A core-shell structure composite metal powder dispersion using the palladium obtained by the above method as a core and silver as a shell, and the platinum particle dispersion obtained by the above method are mixed to mix the core-shell structure. A composite metal powder and a composite metal powder dispersion in which composite metal particle powder and platinum powder particles were mixed were obtained. In mixing, a core-shell structure composite metal powder dispersion with palladium as a core and silver as a shell and a platinum powder dispersion are mixed so that the weight ratio of palladium: silver: platinum is 3:57:40. The sample was collected and stirred and mixed at room temperature with a magnetic stirrer at a rotation speed of 100 rpm.
混合して得られた複合金属粉体は、該コア−シェル構造の複合金属粉体と白金粒子との混合物であり、この混合物中のコア−シェル構造の複合金属粉体は平均粒径ＤTEM＝７．７ｎｍであり、白金粒子は平均粒径ＤTEM＝９．０ｎｍで結晶粒子径Ｄｘ＝７．８ｎｍであり、混合物中のパラジウムと白金を合計した重量割合が４３wt％であった。この混合された複合金属粉体について、本文に記載した方法で特性の評価を行ったところ、エレクトロマイグレーション時間は５秒であり、耐半田喰われ性が良好であることが目視で確認された。 The composite metal powder obtained by mixing is a mixture of the composite metal powder having the core-shell structure and the platinum particles, and the composite metal powder having the core-shell structure in the mixture has an average particle diameter D TEM. = 7.7 nm, the platinum particles had an average particle diameter D TEM = 9.0 nm and a crystal particle diameter Dx = 7.8 nm, and the total weight ratio of palladium and platinum in the mixture was 43 wt%. When this mixed composite metal powder was evaluated for characteristics by the method described herein, it was confirmed by visual observation that the electromigration time was 5 seconds and the solder erosion resistance was good.
〔比較例１〕
液媒体兼還元剤としてのイソブタノール２００ｍＬに、有機保護剤としてオレイルアミンを１３２．７ｍＬと、銀化合物としての硝酸銀結晶を１３．７ｇ添加し、マグネットスターラーにて攪拌して硝酸銀を分散させる。この液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該液をマグネットスターラーにより２００ｒｐｍの回転速度で撹拌しつつ加熱し、１００℃の温度で３時間の還流を行い、反応を終了した。そのさい１００℃に至るまでの昇温速度は２℃／ｍｉｎ とした。
[Comparative Example 1]
To 200 mL of isobutanol as a liquid medium and reducing agent, 132.7 mL of oleylamine as an organic protective agent and 13.7 g of silver nitrate crystals as a silver compound are added, and stirred with a magnetic stirrer to disperse the silver nitrate. This liquid is transferred to a container equipped with a reflux device and placed in an oil bath, and the liquid is stirred at a rotational speed of 200 rpm by a magnetic stirrer while blowing nitrogen gas as an inert gas at a flow rate of 400 mL / min. The mixture was heated and refluxed at a temperature of 100 ° C. for 3 hours to complete the reaction. At that time, the rate of temperature increase up to 100 ° C. was 2 ° C./min.
反応後のスラリーについて本文に記載した洗浄、分散および分級を実施した後、銀粒子粉末分散液を得た。液状有機媒体として、洗浄工程では極性の大きいメタノールを、分散工程では極性の小さいケロシンを使用した。その結果、得られた銀粒子は、平均粒径ＤTEM＝10.3ｎｍであった。この銀粒子粉末を本文に記載した方法で特性の評価を行ったところ、エレクトロマイグレーション時間は１秒であり、耐半田喰われ性が不良であることが確認された。 The slurry after the reaction was washed, dispersed and classified as described in the text, and then a silver particle powder dispersion was obtained. As the liquid organic medium, methanol having a high polarity was used in the washing step, and kerosene having a low polarity was used in the dispersion step. As a result, the resulting silver particles had an average particle diameter D TEM = 10.3 nm. When the characteristics of this silver particle powder were evaluated by the method described herein, it was confirmed that the electromigration time was 1 second and the solder erosion resistance was poor.
Claims (2)
（Ａ）銀と、標準電極電位Ｅ0が０．８０Ｖ以上の銀以外の金属Ｘとの合金の粒子からなり、金属Ｘの重量割合が１〜８０wt％である複合金属粉体であって、当該合金粒子は平均粒径（ＤTEM）が２０ｎｍ以下で且つ結晶粒子径（Ｄｘ）が２０ｎｍ以下である複合金属粉体。 When reducing silver ions and metal X ions into silver particles and metal X particles in one or more liquid organic media of alcohol or polyol that functions as a reducing agent , at least one or more in one molecule A method for producing a composite metal powder that obtains a composite metal powder of the following (A) by controlling the conditions for the reduction reaction in the presence of an amine compound having an unsaturated bond and a molecular weight of 100 to 1000 .
(A) A composite metal powder comprising particles of an alloy of silver and a metal X other than silver having a standard electrode potential E 0 of 0.80 V or more, wherein the weight ratio of the metal X is 1 to 80 wt% , The alloy particles are composite metal powders having an average particle diameter (D TEM ) of 20 nm or less and a crystal particle diameter (Dx) of 20 nm or less.
（Ａ）銀と、標準電極電位Ｅ0が０．８０Ｖ以上の銀以外の金属Ｘとの合金の粒子からなり、金属Ｘの重量割合が１〜８０wt％である複合金属粉体であって、当該合金粒子は平均粒径（ＤTEM）が２０ｎｍ以下で且つ結晶粒子径（Ｄｘ）が２０ｎｍ以下である複合金属粉体。 In the reduction treatment of silver ions and metal X ions into silver particles and metal X particles in one or more liquid organic mediums of alcohol or polyol functioning as a reducing agent, at least one or more in one molecule By controlling the conditions of the reduction reaction in the presence of an amine compound having an unsaturated bond and a molecular weight of 100 to 1000, a composite metal powder of the following (A) is produced, and the resulting composite metal powder has a boiling point of 60 A method for producing a composite metal powder dispersion liquid which is dispersed in a non-polar or small-polar liquid organic medium at ˜300 ° C.
(A) A composite metal powder comprising particles of an alloy of silver and a metal X other than silver having a standard electrode potential E 0 of 0.80 V or more, wherein the weight ratio of the metal X is 1 to 80 wt% , The alloy particles are composite metal powders having an average particle diameter (D TEM ) of 20 nm or less and a crystal particle diameter (Dx) of 20 nm or less.
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