JP4001438B2 - Method for producing composite copper fine powder - Google Patents
Method for producing composite copper fine powder Download PDFInfo
- Publication number
- JP4001438B2 JP4001438B2 JP15275599A JP15275599A JP4001438B2 JP 4001438 B2 JP4001438 B2 JP 4001438B2 JP 15275599 A JP15275599 A JP 15275599A JP 15275599 A JP15275599 A JP 15275599A JP 4001438 B2 JP4001438 B2 JP 4001438B2
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- Prior art keywords
- copper fine
- fine particles
- metal
- composite
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 146
- 229910052802 copper Inorganic materials 0.000 title claims description 144
- 239000010949 copper Substances 0.000 title claims description 144
- 239000002131 composite material Substances 0.000 title claims description 89
- 239000000843 powder Substances 0.000 title claims description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 33
- 239000010419 fine particle Substances 0.000 claims description 71
- 229910052751 metal Inorganic materials 0.000 claims description 56
- 239000011882 ultra-fine particle Substances 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 49
- 239000003985 ceramic capacitor Substances 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 20
- 239000007772 electrode material Substances 0.000 claims description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims description 16
- 150000004706 metal oxides Chemical class 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 description 17
- 239000011164 primary particle Substances 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 11
- 230000000737 periodic effect Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000032798 delamination Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000005065 mining Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 oxides Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 241000282341 Mustela putorius furo Species 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- ZCKXRHNLRWLPLJ-UHFFFAOYSA-N barium(2+);propan-1-olate Chemical compound [Ba+2].CCC[O-].CCC[O-] ZCKXRHNLRWLPLJ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- OEPJXTZQPRTGCX-UHFFFAOYSA-N calcium;propan-1-olate Chemical compound [Ca+2].CCC[O-].CCC[O-] OEPJXTZQPRTGCX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Description
【０００１】
【発明の属する技術分野】
本発明は、積層セラミックコンデンサの内部電極材料及び外部電極材料として用いるのに適した特性を有しており、特に熱収縮特性に優れており、従って大型の積層セラミックコンデンサの製造においてデラミネーション、クラックの発生を防止でき、また厚みの薄いセラミック誘電体と内部電極とからなる小型多層の積層セラミックコンデンサを誘電特性、電気特性を損なうこと無しで製造することを可能とする複合銅微粉末の製造方法に関する。
【０００２】
【従来の技術】
積層セラミックコンデンサは、セラミック誘電体と内部電極とを交互に層状に重ねて圧着し、焼成して一体化させたものであり、このような積層セラミックコンデンサの内部電極を形成する際には、内部電極材料である金属微粉末をペースト化し、該ペーストを用いてセラミック基材上に印刷し、該印刷した基材を複数枚重ねて加熱圧着して一体化した後、還元性雰囲気中で加熱焼成を行うのが一般的である。この内部電極材料として、従来は白金、パラジウムが使用されていたが、近時にはこれら白金、パラジウム等の貴金属の代わりにニッケル、銅等の卑金属を用いる技術が開発され、進歩してきている。
【０００３】
しかしながら、金属銅微粉末を用いた場合には、その粒径にもよるが６００℃近傍より急激な熱収縮を引き起す傾向がある。
積層セラミックコンデンサを作製する際の焼成温度は、セラミック誘電体の構成成分に依存して変化し、ＢａＴｉＯ3 やＳｒＴｉＯ3 等のベロブスカイト型複合酸化物をベースとし、これにガラス材料を添加したり、鉛、ストロンチウム、カルシウム等の酸化物粉添加したりして焼成温度を下げて１０００℃程度で焼結できるような材料も開発されている。
【０００４】
セラミックコンデンサを製造する際の焼結温度を下げることができれば、これまでセラミックコンデンサの内部電極材料として用いていたニッケルよりも安価で導電性の高い銅を用いることができるようになる。また、銅電極材料を用いることにより、近年要求が高まっている高周波用途で低インダクタンスが実現できる。
【０００５】
【発明が解決しようとする課題】
上記のような理由により、積層セラミックコンデンサの製造に用いるペースト用の銅微粉末については、焼成の際のデラミネーションやクラックを抑制するためには、銅微粒子の急激な熱収縮開始温度をより高温側へシフトさせてセラミック基材の熱収縮曲線に近づけることが重要視される。
【０００６】
本発明は、積層セラミックコンデンサの内部電極材料として用いるのに適した特性を有しており、特に、セラミック基材の熱収縮曲線に近い熱収縮特性を有しており、従って大型の積層セラミックコンデンサの製造においてデラミネーション、クラックの発生を防止でき、また厚みの薄いセラミック誘電体と内部電極とからなる小型多層の積層セラミックコンデンサを誘電特性、電気特性を損なうこと無しで製造することを可能とする複合銅微粉末の製造方法を提供することを課題としている。
【０００７】
【課題を解決するための手段】
本発明者らは上記の課題を達成するために鋭意研究を重ねた結果、金属銅微粒子表面に金属元素の酸化物及び／又は複合酸化物を固着させることにより上記の特性を有する複合銅微粉末が得られること、並びにそのような複合銅微粉末が湿式担持法、乾式担持法及び半乾式担持法の何れによっても製造できることを見いだし、本発明を完成した。
【０００９】
即ち、本発明のセラミックコンデンサ用電極材料用複合銅微粉末の製造方法は、平均粒径が３μｍ以下の金属銅微粒子又は表面を酸化処理した金属銅微粒子が液中に分散しているスラリーに、金属元素、好ましくは原子番号が１２〜４２、５６〜７５及び８２の範囲内で周期表の２〜１４族に属する金属元素の水溶性塩からなる群より選ばれる少なくとも１種を含む水溶液を添加し、次いで酸もしくはアルカリでｐＨを調整して、該水溶性塩から誘導される金属酸化物及び／又は複合酸化物を該銅微粒子表面に固着させ、洗浄し、乾燥させ、得られた金属酸化物及び／又は複合酸化物が固着している該銅微粒子を相互に又は他物体と衝突させて該銅微粒子の表面と該金属酸化物及び／又は複合酸化物との固着を増強させることを特徴とする。
【００１０】
更に、本発明のセラミックコンデンサ用電極材料用複合銅微粉末の製造方法は、平均粒径が３μｍ以下の金属銅微粒子又は表面を酸化処理した金属銅微粒子の表面に、金属元素、好ましくは原子番号が１２〜４２、５６〜７５及び８２の範囲内で周期表の２〜１４族に属する金属元素の少なくとも１種を含む酸化物及び複合酸化物からなる平均粒径が０．５μｍ以下の超微粒子からなる群より選ばれる少なくとも１種を付着させ、該超微粒子の付着している銅微粒子を相互に又は他物体と衝突させて該銅微粒子の表面に該超微粒子を固着させることを特徴とする。
【００１１】
また、本発明のセラミックコンデンサ用電極材料用複合銅微粉末の製造方法は、金属元素、好ましくは原子番号が１２〜４２、５６〜７５及び８２の範囲内で周期表の２〜１４族に属する金属元素の少なくとも１種を含む酸化物及び複合酸化物からなる平均粒径が０．５μｍ以下の超微粒子からなる群より選ばれる少なくとも１種を懸濁させた懸濁液と、平均粒径が３μｍ以下の金属銅微粒子又は表面を酸化処理した金属銅微粒子とを混合しながら加熱し、該懸濁液の媒体を除去して、該銅微粒子の表面に該超微粒子を付着させ、該超微粒子の付着している銅微粒子を相互に又は他物体と衝突させて該銅微粒子の表面に該超微粒子を固着させることを特徴とする。
【００１２】
【発明の実施の形態】
本発明の製造方法で得られるセラミックコンデンサ用電極材料用複合銅微粉末（以下、本発明の複合銅微粉末という）においては、金属銅微粒子表面に、金属元素、好ましくは原子番号が１２〜４２、５６〜７５及び８２の範囲内で周期表の２〜１４族に属する金属元素の少なくとも１種を含む酸化物及び複合酸化物からなる群より選ばれる少なくとも１種が固着しているので、本発明の複合銅微粉末はセラミック基材の熱収縮曲線に近い熱収縮特性を有しており、従って大型の積層セラミックコンデンサの製造においてデラミネーション、クラックの発生を防止することができる。また、厚みの薄いセラミック誘電体と内部電極とからなる小型多層の積層セラミックコンデンサを誘電特性、電気特性を損なうこと無しで製造することが可能である。
【００１３】
本発明の複合銅微粉末を含有するペーストを内部電極の形成に用いて、小型多層の積層セラミックコンデンサを誘電特性、電気特性を損うこと無しで製造するためには、好ましくは原子番号が１２〜４２、５６〜７５及び８２の範囲内で周期表の２〜１４族に属する金属元素の少なくとも１種を含む酸化物及び複合酸化物からなる群より選ばれる少なくとも１種が固着している複合銅微粉末を用い、より好ましくは原子番号が１２〜４２、５６〜７５及び８２の範囲内で周期表の２〜４族、７族、１３族及び１４族に属する金属元素の少なくとも１種を含む酸化物及び複合酸化物からなる群より選ばれる少なくとも１種が固着している複合銅微粉末を用いる。
【００１４】
更に、周期表の２族に属する金属元素、Ｙ、Ｚｒ、Ｍｎ、Ａｌ、Ｓｉ又はランタノイド元素の酸化物からなる群より選ばれる少なくとも１種が固着している複合銅微粉末及を用いることが好ましい。
また、上記の複合酸化物として後記の複合酸化物を含めて種々のものが使用可能である。
本発明の複合銅微粉末は、積層セラミックコンデンサの内部電極材料として用いる場合には、積層セラミックコンデンサの誘電体の組成と同一の組成を持つ複合酸化物が銅微粒子表面に固着しているものであることが好ましい。
【００１５】
本発明の複合銅微粉末においては、積層セラミックコンデンサの内部電極材料として用いる場合には、金属銅微粒子表面に、一般式
Ｂａm Ｘ1-m Ｔｉn Ｚ1-n Ｏ3
（式中、ＸはＳｒ、Ｃａ、Ｍｇ又はＰｂであり、ＺはＺｒ、Ｙ、Ｓｎ又はＧｅであり、ｍは０〜１の範囲内の値であり、ｎは０〜１の範囲内の値である。）
で示される複合酸化物からなる群より選ばれる少なくとも１種が固着していることが好ましく、それらの複合酸化物は１種単独で固着させても、２種以上を併用して固着させてもよく、あるいはそれらの複合酸化物を主成分とし、添加成分として上記の種々の酸化物の少なくとも１種を用いて固着させてもよい。
【００１６】
上記の酸化物及び複合酸化物としては、例えば、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ａｌ2 Ｏ3 、Ｇａ2 Ｏ3 、Ｙ2 Ｏ3 、ＳｉＯ2 、ＴｉＯ2 、ＺｒＯ2 、Ｃｒ2 Ｏ3 、ＭｎＯ2 、Ｍｎ3 Ｏ4 、Ｎｂ2 Ｏ5 、ＢａＴｉＯ3 、ＣａＴｉＯ3 、ＳｒＴｉＯ3 、ＢａＺｒＯ3 、ＣａＺｒＯ3 、ＳｒＺｒＯ3 、（Ｍｇ，Ｃａ）ＴｉＯ3 、（Ｂａ，Ｃａ）（Ｔｉ，Ｚｒ）Ｏ3 、ＰｂＴｉＯ3 、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3 、（Ｐｂ，Ｃａ）ＴｉＯ3 、ＭｇＡｌ2 Ｏ4 、ＢａＴｉ4 Ｏ9 、Ｎｄ2 Ｏ3 、Ｓｍ2 Ｏ3 、Ｄｙ2 Ｏ3 、Ｅｒ2 Ｏ3 、Ｈｏ2 Ｏ3 等を挙げることができ、それらは混合物として用いることも出来る。更にこれらの酸化物及び／又は複合酸化物はＮｂ、Ｗ、Ｌａ、Ｙ、Ｍｏ等の金属の酸化物でドープされていてもよい。
【００１７】
本発明の複合銅微粉末においては、該複合銅微粉末を積層セラミックコンデンサの内部電極を形成するペーストに用いる場合には微細である方が微細な電極を形成できるので望ましく、具体的にはＳＥＭ観察による銅微粉末の平均粒径が３μｍ以下であることが好ましく、１μｍ以下であることがより好ましい。金属微粉末は、一般的には、微細になればなるほど熱収縮を起こし易いが、本発明の複合銅微粉末においては、微細になっても熱収縮防止効果が発揮されるので、その効果はますます顕著となる。
【００１８】
また、これらの酸化物及び複合酸化物からなる群より選ばれる少なくとも１種の合計固着量は銅微粉末の重量に対して好ましくは０．０５〜１５重量％、より好ましくは０．５〜１３重量％、更に好ましくは１〜１０重量％である。合計固着量が０．０５重量％未満の場合には、酸化物及び／又は複合酸化物の固着によって達成される効果が不十分となる傾向があり、逆に１５重量％を越える場合には、そのような複合銅微粉末を積層セラミックコンデンサの内部電極材料として使用したときに、コンデンサの誘電特性に悪影響を及ぼす傾向がある。
【００１９】
本発明の複合銅微粉末の製造方法で用いる銅微粒子又は表面を酸化処理した銅微粒子は、機械的粉砕法、アトマイズ法、電解析出法、蒸発法、湿式還元法等の何れの方法によって得られたものであってもよい。本発明の複合銅微粉末を積層セラミックコンデンサの内部電極を形成するペーストに用いる場合には、その製造に用いる銅微粒子の平均粒径が３μｍ以下であることが好ましく、１μｍ以下であることがより好ましい。
【００２０】
本発明の複合銅微粉末は湿式担持法又は乾式担持法によって、或いは金属酸化物又は複合酸化物の超微粒子の水性懸濁液を金属銅微粒子に担持させて乾燥する半乾式担持法によって製造することができる。
湿式担持法に従って実施する場合の本発明の複合銅微粉末の製造方法においては、金属銅微粒子又は表面を酸化処理した金属銅微粒子が液中に分散しているスラリーに、金属元素、好ましくは原子番号が１２〜４２、５６〜７５及び８２の範囲内で周期表の２〜１４族に属する金属元素の水溶性塩からなる群より選ばれる少なくとも１種を含む水溶液を添加し、次いで酸もしくはアルカリでｐＨを調整して、該水溶性塩から誘導される金属酸化物及び／又は複合酸化物を該銅微粒子表面に固着させ、洗浄し、乾燥させ、得られた金属酸化物及び／又は複合酸化物が固着している該銅微粒子を相互に又は他物体と衝突させて該銅微粒子の表面と該金属酸化物及び／又は複合酸化物との固着を増強させる。
【００２１】
湿式担持法に従って実施する場合の本発明の複合銅微粉末の製造方法で用いる上記の水溶性塩は水溶性であるが、水不溶性の酸化物又は複合酸化物に転化できるものであれば特には制限されない。例えば、これらの金属元素のハロゲン化物、硝酸塩、硫酸塩、蓚酸塩、酸化物や、アルミン酸、ケイ酸等のアルカリ金属塩等を用いることができる。
【００２２】
湿式担持法に従って実施する場合の本発明の複合銅微粉末の製造方法においては、ｐＨを調整するために酸を用いるかアルカリを用いるかは上記の水溶性塩の種類に応じて変化するが、用いる酸又はアルカリの種類については特には限定されない。例えば、下記の水溶性塩を用いて括弧内の酸化物を生成させる場合には水酸化ナトリウム水溶液を使用することができる。
硫酸チタン（ＴｉＯ2 ）、硫酸マンガン（ＭｎＯ2 ）、
塩化クロム（Ｃｒ2 Ｏ3 ）、塩化イットリウム（Ｙ2 Ｏ3 ）、
塩化酸化ジルコニウム（ＺｒＯ2 ）。
また、下記の水溶性塩を用いて括弧内の酸化物を生成させる場合には希硫酸を使用することができる。
アルミン酸ナトリウム（Ａｌ2 Ｏ3 ）、ケイ酸ナトリウム（ＳｉＯ2 ）。
上記のようにｐＨを調整することにより、上記の水溶性塩が酸化物や複合酸化物に転化して銅微粒子表面に析出し、固着して本発明の複合銅微粉末となる。
【００２３】
湿式担持法に従って実施する場合の本発明の複合銅微粉末の製造方法においては、金属酸化物及び／又は複合酸化物が固着している該銅微粒子を相互に又は他物体と衝突させて該銅微粒子の表面と該金属酸化物及び／又は複合酸化物との固着を増強させる工程を、例えば、オングミル、ハイブリタイザー、メカノフュージョン、コートマイザー、ディスパーコート、ジェットマイザーのいずれかの装置で処理することにより実施できる。
【００２４】
乾式担持法に従って実施する場合の本発明の複合銅微粉末の製造方法においては、金属銅微粒子又は表面を酸化処理した金属銅微粒子の表面に、金属元素、好ましくは原子番号が１２〜４２、５６〜７５及び８２の範囲内で周期表の２〜１４族に属する金属元素の少なくとも１種を含む酸化物及び複合酸化物の超微粒子からなる群より選ばれる少なくとも１種を付着させ、該超微粒子の付着している銅微粒子を相互に又は他物体と衝突させて該銅微粒子の表面に該超微粒子を固着させることができる。
【００２５】
乾式担持法に従って実施する場合の本発明の複合銅微粉末の製造方法で用いる金属銅微粒子又は表面を酸化処理した金属銅微粒子は、本発明の複合銅微粉末を積層セラミックコンデンサの内部電極を形成するためのペーストとして用いる場合には、平均粒径が３μｍ以下であることが好ましく、１μｍ以下であることがより好ましい。また、酸化物、複合酸化物の超微粒子は、粒径が小さいほど少量で均一に固着させることができるので、平均粒径が０．５μｍ以下であることが好ましく、０．１μｍ以下であることがより好ましく、０．０５μｍ以下であることが最も好ましい。
【００２６】
金属銅微粒子又は表面を酸化処理した金属銅微粒子の表面に酸化物、複合酸化物の超微粒子を固着させる方法としては、該金属銅微粒子と該酸化物、複合酸化物の超微粒子とを混合し、その後、該超微粒子の付着している銅微粒子を相互に又は他物体と衝突させて該銅微粒子の表面に該超微粒子を固着させることもできる。その他の方法としては、オングミル、ハイブリタイザー、メカノフュージョン、コートマイザー、ディスパーコート、ジェットマイザー等の装置中に該銅微粒子と該酸化物や複合酸化物の超微粒子とを装入し、混合と固着とを同時に実施することもできる。
【００２７】
半乾式担持法に従って実施する場合の本発明の複合銅微粉末の製造方法においては、金属元素、好ましくは原子番号が１２〜４２、５６〜７５及び８２の範囲内で周期表の２〜１４族に属する金属元素の少なくとも１種を含む酸化物及び複合酸化物の超微粒子からなる群より選ばれる少なくとも１種を懸濁させた懸濁液と、金属銅微粒子又は表面を酸化処理した金属銅微粒子とを混合しながら加熱し、該懸濁液の媒体を除去して、該銅微粒子の表面に該超微粒子を付着させ、該超微粒子の付着している銅微粒子を相互に又は他物体と衝突させて該銅微粒子の表面に該超微粒子を固着させることができる。
【００２８】
上記の半乾式担持法で用いる金属銅微粒子又は表面を酸化処理した金属銅微粒子、並びに酸化物及び複合酸化物の超微粒子は上記の乾式担持法で用いるものと同一でよい。また、超微粒子を懸濁させる媒体は特には限定されず、一般的には水、酸性水溶液、塩基性水溶液、アルコール、有機溶媒等を用いることができる。この製造方法においては所定固形分濃度の懸濁液を調製して用いても、或いは、市販品のシリカゾル、アルミナゾル、チタニアゾル、チタン酸バリウムゾル等を用い、必要に応じて希釈などを行って濃度を調整して用いてもよい。
【００２９】
以下に、実施例、比較例及び製造例によって本発明を具体的に説明するが、本発明はかかる事例に限定されるものではない。
実施例１〜８
銅微粉末（三井金属鉱業株式会社製１０５０Ｙ、平均１次粒径約０．５μｍ）５００ｇと、超微粒のアルミナ（日本アエロジル社製酸化アルミニウムＣ、平均１次粒径１３ｎｍ）、酸化珪素（日本アエロジル社製３００ＣＦ、平均１次粒径７ｎｍ）、酸化イットリウム（シーアイ化成社製、平均１次粒径１０ｎｍ）、酸化マグネシウム（宇部マテリアル社製１００Ａ、平均１次粒径１０ｎｍ）、チタン酸バリウム（チタニウムプロポキシドとバリウムプロポキシドを用いてゾルゲル法により調製、平均１次粒径３０ｎｍ）、又は酸化チタン（日本アエロジル社製Ｐ２５、平均１次粒径１３ｎｍ）のうちのいずれか２５ｇ（銅微粉末に対する混合率５重量％）又は５ｇ（銅微粉末に対する混合率１重量％）とを１５分間攪拌混合した。これにより表面に上記の各超微粒子の何れかが付着している銅微粒子を得た。更にこれをハイブリタイザー（奈良機械製作所製）に投入し、８０００ｒｐｍで５分間循環させて、銅微粒子表面に上記の各超微粒子の何れかが固着された複合銅微粉末を得た。
【００３０】
得られた各々の複合銅微粉末においては、金属銅微粒子表面に各超微粒子が固着されているので、水中に投入して攪拌しても各超微粒子が剥離・浮遊することはなかった（単に攪拌しただけのものでは各超微粒子が浮遊して水が白濁した）。また各超微粒子が固着された該複合銅微粉末は、ＳＥＭ観察の結果、表面に各超微粒子が均一に固着されていること、及び粒径はほとんど変化していないことが確認された。
【００３１】
上記の実施例１〜８で得られた複合銅微粉末を熱機械分析装置（セイコー電子工業製ＴＭＡ／ＳＳ６０００）を用いて窒素ガス雰囲気中、昇温速度１０℃／分で熱収縮率を測定した。それらの結果は第１表に示す通りであった。
なお、比較例１として未処理銅微粉末（三井金属鉱業株式会社製１０５０Ｙ、平均１次粒径約０．５μｍ）についても同様にして熱収縮率を測定した。その結果も第１表に示す。なお、比較例１では９００℃を超えた時点より銅微粉末の溶融が始まったためその時点で昇温を中断し、熱収縮率を測定したところ、−１５％であった。
【００３２】
第１表のデータから明らかなように、実施例１〜８の本発明の複合銅微粉末は、比較例１の未処理の銅微粉末と比較して、高温での熱収縮率が極めて小さくなっている。
【００３４】
実施例９
実施例１で用いたハイブリタイザー（奈良機械製作所製）の代わりにメカノフュージョン（ホソカワミクロン製）を用い、３０００ｒｐｍで３０分間循環させた以外は実施例１と同様にして、銅微粒子表面にアルミナ超微粒子が固着された複合銅微粉末を得た。
【００３５】
得られた該複合銅微粉末においてはアルミナ超微粒子が固着されているので、水中に投入して攪拌してもアルミナ超微粒子が剥離・浮遊することはなかった。またアルミナ超微粒子が固着された該複合銅微粉末は、ＳＥＭ観察の結果、表面にアルミナ超微粒子が均一に固着されていること、及び粒径はほとんど変化していないことが確認された。
【００３６】
実施例１０〜１２
銅微粉末（三井金属鉱業株式会社製１０５０Ｙ、平均１次粒径約０．５μｍ）５００ｇと、超微粒のチタン酸ストロンチウム（ゾルゲル法によって調製、平均１次粒径１０ｎｍ）、チタン酸バリウムストロンチウム（Ba0.9Sr0.1)TiO3 （ゾルゲル法によって調製、平均１次粒径１０ｎｍ）、又はジルコニア酸カルシウム（ジルコニウムプロポキシド及びジプロポキシカルシウムを用いてゾルゲル法によって調製、平均１次粒径３０ｎｍ）のうちのいずれか５ｇ（銅微粉末に対する混合率１重量％）とを１５分間攪拌混合した。これにより表面に上記の各超微粒子の何れかが付着している銅微粒子を得た。更にこれをハイブリタイザー（奈良機械製作所製）に投入し、８０００ｒｐｍで５分間循環させて、銅微粒子表面に上記の各超微粒子の何れかが固着された複合銅微粉末を得た。
【００３７】
得られた各々の複合銅微粉末においては、金属銅微粒子表面に各超微粒子が固着されているので、水中に投入して攪拌しても各超微粒子が剥離・浮遊することはなかった。また、各超微粒子が固着された該複合銅微粉末は、ＳＥＭ観察の結果、表面に各超微粒子が均一に固着されていること、及び粒径はほとんど変化していないことが確認された。更に、実施例１０〜１２の本発明の複合銅微粉末は実施例７とほぼ同じような熱収縮率を示した。
【００３８】
製造例１
銅微粉末（三井金属鉱業株式会社製１０５０Ｙ、平均１次粒径約１μｍ）１００ｇを純水１リットル中に加え、攪拌してスラリー化した。３０分間攪拌した後、過酸化水素水１００ｇを一括添加した。反応が終了して泡が出なくなった時点で攪拌を停止し、濾過し、乾燥して、表面を酸化処理した銅微粉末を得た。得られた銅微粒子のＳＥＭ観察による平均粒径（フェレ径）は１μｍであった。
【００４５】
実施例１３
シリカゾル（日産化学社製、スノーテックスＯ、平均１次粒径約１０ｎｍ）を水で１／２０に希釈した溶液（シリカ含有量１０ｇ／ｌ）２．５リットルに、銅微粉末（三井金属鉱業株式会社製１０５０Ｙ、平均１次粒径約０．５μｍ）５００ｇを入れ、加熱しながら良く攪拌した。水分は徐々に気化し、最後に乾燥粉体が得られた。これをハイブリタイザー（奈良機械製作所製）に投入し、８０００ｒｐｍで５分間循環させて、銅微粒子表面にシリカ超微粒子が固着された複合銅微粉末を得た。
【００４６】
実施例１３で得られた本発明の複合銅微粉末においては、ＳＥＭ観察の結果、表面にシリカ超微粒子が均一に固着されていること、及び粒径はほとんど変化していないことが確認された。得られた各複合銅微粉末においては超微粒子が固着されているので、水中に投入して攪拌しても超微粒子が剥離・浮遊することはなかった。また、各複合銅微粉末は、固着している金属酸化物の種類に応じて実施例１〜６、８と類似の熱収縮率を示した。
【００４７】
【発明の効果】
上記のように本発明による複合銅微粉末は、急激な熱収縮開始温度が１０００℃付近にシフトしており、積層コンデンサの内部電極形成用途に極めて好適である。即ち、セラミック基材の熱収縮曲線に近い熱収縮特性を有しており、従って大型の積層セラミックコンデンサの製造においてデラミネーション、クラックの発生を防止でき、また厚みの薄いセラミック誘電体と内部電極とからなる小型多層の積層セラミックコンデンサを誘電特性、電気特性を損なうこと無しで製造することがを可能となる。また、銅電極材料を用いることにより、近年要求が高まっている高周波用途で低インダクタンスが実現できる。[0001]
BACKGROUND OF THE INVENTION
The present invention has characteristics suitable for use as an internal electrode material and an external electrode material of a multilayer ceramic capacitor, and is particularly excellent in heat shrinkage characteristics. Therefore, in the production of a large multilayer ceramic capacitor, delamination and cracks are produced. the method of generating can be prevented, also dielectric properties of the multilayer ceramic capacitor of small multi-layer consisting of a thin ceramic dielectric and internal electrode thicknesses, possible to produce in without impairing the electrical characteristics to the powder composite copper fine manufacturing About.
[0002]
[Prior art]
Multilayer ceramic capacitors are ceramic dielectrics and internal electrodes that are alternately layered and pressure-bonded and then fired and integrated. When forming such multi-layer ceramic capacitors, Metal fine powder, which is an electrode material, is made into a paste, printed on the ceramic substrate using the paste, and a plurality of the printed substrates are stacked and integrated by thermocompression bonding, and then heated and fired in a reducing atmosphere. It is common to do. Conventionally, platinum and palladium have been used as the internal electrode material. Recently, techniques using base metals such as nickel and copper instead of noble metals such as platinum and palladium have been developed and advanced.
[0003]
However, when metal copper fine powder is used, it tends to cause rapid thermal shrinkage from around 600 ° C., although it depends on the particle size.
The firing temperature at the time of manufacturing the multilayer ceramic capacitor varies depending on the components of the ceramic dielectric, and is based on a velovskite complex oxide such as BaTiO 3 or SrTiO 3 , and a glass material is added to this. Materials that can be sintered at about 1000 ° C. by adding oxide powder such as lead, strontium, calcium, etc. to lower the firing temperature have been developed.
[0004]
If the sintering temperature at the time of manufacturing the ceramic capacitor can be lowered, copper that is cheaper and has higher conductivity than nickel that has been used as the internal electrode material of the ceramic capacitor can be used. Further, by using a copper electrode material, a low inductance can be realized in high frequency applications that have been increasingly demanded in recent years.
[0005]
[Problems to be solved by the invention]
For the above reasons, the copper fine powder for paste used in the production of multilayer ceramic capacitors has a higher heat shrinkage start temperature of copper fine particles in order to suppress delamination and cracks during firing. It is important to make the shift closer to the heat shrinkage curve of the ceramic substrate.
[0006]
The present invention has characteristics suitable for use as an internal electrode material of a multilayer ceramic capacitor, and in particular, has a heat shrinkage characteristic close to the heat shrinkage curve of a ceramic substrate, and therefore, a large multilayer ceramic capacitor. Can prevent the occurrence of delamination and cracks, and enables the production of small multilayer multilayer ceramic capacitors consisting of thin ceramic dielectrics and internal electrodes without impairing dielectric and electrical characteristics. It aims at providing the manufacturing method of composite copper fine powder.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned problems, the present inventors have obtained a composite copper fine powder having the above-mentioned characteristics by fixing the metal element oxide and / or composite oxide on the surface of the metal copper fine particles. And that the composite copper fine powder can be produced by any one of the wet loading method, the dry loading method and the semi-dry loading method, thereby completing the present invention.
[0009]
That is, the method for producing a composite copper fine powder for an electrode material for a ceramic capacitor according to the present invention is a slurry in which metal copper fine particles having an average particle size of 3 μm or less or metal copper fine particles whose surface is oxidized are dispersed in a liquid. Addition of an aqueous solution containing a metal element, preferably at least one selected from the group consisting of water-soluble salts of metal elements belonging to groups 2-14 of the periodic table within the range of atomic numbers 12-42, 56-75 and 82 Then, the pH is adjusted with acid or alkali to fix the metal oxide and / or composite oxide derived from the water-soluble salt to the surface of the copper fine particles, washed and dried, and the obtained metal oxide The copper fine particles to which the object and / or the composite oxide are fixed collide with each other or other objects to enhance the adhesion between the surface of the copper fine particles and the metal oxide and / or the composite oxide. And
[0010]
Furthermore, the method for producing a composite copper fine powder for an electrode material for a ceramic capacitor according to the present invention comprises a metal element, preferably an atomic number, on the surface of metal copper fine particles having an average particle diameter of 3 μm or less or metal copper fine particles obtained by oxidizing the surface. Is an ultrafine particle having an average particle size of 0.5 μm or less, comprising an oxide containing at least one metal element belonging to Group 2-14 of the periodic table in the range of 12 to 42, 56 to 75 and 82 and a composite oxide At least one selected from the group consisting of: and attaching the ultrafine particles to the surface of the copper fine particles by causing the ultrafine particles to collide with each other or with other objects. .
[0011]
Moreover, the manufacturing method of the composite copper fine powder for electrode materials for ceramic capacitors of this invention belongs to the 2-14 group of a periodic table within the range of a metal element, Preferably atomic number is 12-42, 56-75, and 82. A suspension in which at least one selected from the group consisting of an ultrafine particle having an average particle size of 0.5 μm or less composed of an oxide containing at least one metal element and a composite oxide is suspended; Heating while mixing metal copper fine particles of 3 μm or less or metal copper fine particles whose surface is oxidized, removing the suspension medium, attaching the ultrafine particles to the surface of the copper fine particles, The ultrafine particles are fixed on the surface of the copper fine particles by colliding with each other or with other objects.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
In the composite copper fine powder for electrode materials for ceramic capacitors obtained by the production method of the present invention (hereinafter referred to as the composite copper fine powder of the present invention), a metal element, preferably an atomic number of 12 to 42, is formed on the surface of the metal copper fine particles. In the range of 56 to 75 and 82, at least one selected from the group consisting of oxides and composite oxides containing at least one metal element belonging to Group 2-14 of the periodic table is fixed. The composite copper fine powder of the invention has a heat shrinkage characteristic close to the heat shrinkage curve of the ceramic substrate, and therefore it is possible to prevent the occurrence of delamination and cracks in the production of a large multilayer ceramic capacitor. Further, it is possible to manufacture a small multilayer multilayer ceramic capacitor composed of a thin ceramic dielectric and an internal electrode without impairing dielectric characteristics and electrical characteristics.
[0013]
In order to produce a small-sized multilayer monolithic ceramic capacitor without deteriorating dielectric properties and electrical properties using the paste containing the composite copper fine powder of the present invention for the formation of internal electrodes, the atomic number is preferably 12 A composite in which at least one selected from the group consisting of oxides and composite oxides containing at least one metal element belonging to Group 2 to 14 of the periodic table in the range of ˜42, 56 to 75 and 82 is fixed. Using copper fine powder, more preferably at least one metal element belonging to groups 2-4, 7, 13, 13 and 14 of the periodic table in the range of atomic numbers 12-42, 56-75 and 82 The composite copper fine powder to which at least 1 sort (s) chosen from the group which consists of an oxide and complex oxide to contain is adhering is used.
[0014]
Furthermore, it is preferable to use a composite copper fine powder to which at least one selected from the group consisting of oxides of metal elements belonging to Group 2 of the periodic table, Y, Zr, Mn, Al, Si or lanthanoid elements is fixed. preferable.
Moreover, various things can be used as said complex oxide including the complex oxide of a postscript.
When the composite copper fine powder of the present invention is used as an internal electrode material of a multilayer ceramic capacitor, a composite oxide having the same composition as the dielectric composition of the multilayer ceramic capacitor is fixed to the surface of the copper fine particles. Preferably there is.
[0015]
In composite copper fine powder of the present invention, when used as an internal electrode material for multilayer ceramic capacitors, the metallic copper fine particle surface, the general formula Ba m X 1-m Ti n Z 1-n O 3
Wherein X is Sr, Ca, Mg or Pb, Z is Zr, Y, Sn or Ge, m is a value in the range of 0 to 1, and n is in the range of 0 to 1. Value.)
It is preferable that at least one selected from the group consisting of the complex oxides shown in the above is fixed, and these complex oxides may be fixed alone or in combination of two or more. Alternatively, the composite oxide may be used as a main component, and the additive may be fixed using at least one of the various oxides as an additive component.
[0016]
Examples of the oxide and composite oxide include MgO, CaO, SrO, BaO, ZnO, Al 2 O 3 , Ga 2 O 3 , Y 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , and Cr 2 O. 3 , MnO 2 , Mn 3 O 4 , Nb 2 O 5 , BaTiO 3 , CaTiO 3 , SrTiO 3 , BaZrO 3 , CaZrO 3 , SrZrO 3 , (Mg, Ca) TiO 3 , (Ba, Ca) (Ti, Zr) ) O 3 , PbTiO 3 , Pb (Zr, Ti) O 3 , (Pb, Ca) TiO 3 , MgAl 2 O 4 , BaTi 4 O 9 , Nd 2 O 3 , Sm 2 O 3 , Dy 2 O 3 , Er 2 O 3 , Ho 2 O 3 and the like can be mentioned, and they can also be used as a mixture. Further, these oxides and / or composite oxides may be doped with metal oxides such as Nb, W, La, Y, and Mo.
[0017]
In the composite copper fine powder of the present invention, when the composite copper fine powder is used in a paste for forming an internal electrode of a multilayer ceramic capacitor, it is desirable that the fine powder is fine, because a fine electrode can be formed. The average particle diameter of the copper fine powder as observed is preferably 3 μm or less, and more preferably 1 μm or less. In general, metal fine powders are more likely to undergo thermal shrinkage as they become finer. However, in the composite copper fine powder of the present invention, the effect of preventing thermal shrinkage is exhibited even if it becomes finer. Increasingly prominent.
[0018]
The total fixed amount of at least one selected from the group consisting of these oxides and composite oxides is preferably 0.05 to 15% by weight, more preferably 0.5 to 13%, based on the weight of the copper fine powder. % By weight, more preferably 1 to 10% by weight. When the total fixing amount is less than 0.05% by weight, the effect achieved by the fixing of the oxide and / or composite oxide tends to be insufficient, and conversely when it exceeds 15% by weight, When such a composite copper fine powder is used as an internal electrode material of a multilayer ceramic capacitor, it tends to adversely affect the dielectric characteristics of the capacitor.
[0019]
The copper fine particles used in the method for producing the composite copper fine powder of the present invention or the copper fine particles obtained by oxidizing the surface can be obtained by any method such as a mechanical pulverization method, an atomization method, an electrolytic deposition method, an evaporation method, and a wet reduction method. It may be what was made. When the composite copper fine powder of the present invention is used as a paste for forming an internal electrode of a multilayer ceramic capacitor, the average particle size of the copper fine particles used for the production is preferably 3 μm or less, more preferably 1 μm or less. preferable.
[0020]
The composite copper fine powder of the present invention is produced by a wet support method or a dry support method, or a semi-dry support method in which an aqueous suspension of metal oxide or composite oxide ultrafine particles is supported on metal copper fine particles and dried. be able to.
In the method for producing a composite copper fine powder of the present invention when carried out according to the wet support method, metal elements, preferably atoms, are added to the slurry in which the metal copper fine particles or the metal copper fine particles whose surface is oxidized are dispersed in the liquid. An aqueous solution containing at least one selected from the group consisting of water-soluble salts of metal elements belonging to groups 2 to 14 of the periodic table within the range of numbers 12 to 42, 56 to 75 and 82, and then acid or alkali The metal oxide and / or composite oxide derived from the water-soluble salt is fixed to the surface of the copper fine particles , washed and dried, and the resulting metal oxide and / or composite oxidation is adjusted. things Ru enhanced the adhesion between the surface and the metal oxide and / or composite oxide of the copper fine particles with each other or other object and to collide with copper microparticles are fixed.
[0021]
The water-soluble salt used in the method for producing a composite copper fine powder according to the present invention when carried out according to the wet support method is water-soluble, but particularly if it can be converted into a water-insoluble oxide or composite oxide. Not limited. For example, halides of these metal elements, nitrates, sulfates, oxalates, oxides, alkali metal salts such as aluminate and silicic acid, and the like can be used.
[0022]
In the production method of the composite copper fine powder of the present invention when carried out according to the wet loading method, whether to use an acid or an alkali to adjust the pH varies depending on the type of the water-soluble salt, The type of acid or alkali used is not particularly limited. For example, an aqueous sodium hydroxide solution can be used when an oxide in parentheses is generated using the following water-soluble salt.
Titanium sulfate (TiO 2 ), manganese sulfate (MnO 2 ),
Chromium chloride (Cr 2 O 3 ), yttrium chloride (Y 2 O 3 ),
Zirconium chloride (ZrO 2 ).
In addition, dilute sulfuric acid can be used when an oxide in parentheses is generated using the following water-soluble salt.
Sodium aluminate (Al 2 O 3 ), sodium silicate (SiO 2 ).
By adjusting the pH as described above, the above-mentioned water-soluble salt is converted into an oxide or composite oxide, precipitated on the surface of the copper fine particles, and fixed to form the composite copper fine powder of the present invention.
[0023]
In the method for producing a composite copper fine powder according to the present invention when carried out according to the wet loading method, the copper fine particles to which the metal oxide and / or the composite oxide are fixed collide with each other or with other objects, and the copper The step of enhancing the adhesion between the surface of the fine particles and the metal oxide and / or the composite oxide is treated with , for example, any of an ongmill, a hybridizer, a mechanofusion, a coater, a dispercoat, and a jetmizer. Can be implemented .
[0024]
In the method for producing a composite copper fine powder of the present invention when carried out according to the dry support method, a metal element, preferably an atomic number of 12 to 42, 56 is formed on the surface of the metal copper fine particles or the metal copper fine particles obtained by oxidizing the surface. At least one selected from the group consisting of oxides containing at least one metal element belonging to Group 2-14 of the periodic table in the range of ~ 75 and 82 and ultrafine particles of complex oxides is adhered, and the ultrafine particles The ultrafine particles can be fixed to the surface of the copper fine particles by colliding with each other or with other objects.
[0025]
The metal copper fine particles used in the method for producing the composite copper fine powder of the present invention when carried out according to the dry support method or the metal copper fine particles whose surface is subjected to oxidation treatment form the internal electrode of the multilayer ceramic capacitor by using the composite copper fine powder of the present invention. When used as a paste for this purpose, the average particle size is preferably 3 μm or less, and more preferably 1 μm or less. In addition, since the ultrafine particles of oxide and composite oxide can be uniformly fixed in a smaller amount as the particle size is smaller, the average particle size is preferably 0.5 μm or less, preferably 0.1 μm or less. Is more preferable, and most preferably 0.05 μm or less.
[0026]
As a method of adhering the ultrafine particles of the oxide and composite oxide to the surface of the metal copper fine particles or the surface of the metal copper fine particles oxidized by oxidation, the metal copper fine particles and the oxide and ultrafine particles of the composite oxide are mixed. Thereafter, the ultrafine particles can also be fixed to the surface of the copper fine particles by colliding with each other or with other objects. As another method, the copper fine particles and ultrafine particles of the oxide or composite oxide are charged into an apparatus such as ong mill, hybridizer, mechano-fusion, coat mizer, disperse coat, jet mizer, and mixed and fixed. Can be performed simultaneously.
[0027]
In the method for producing the composite copper fine powder of the present invention when carried out according to the semi-dry support method, the metal elements, preferably the atomic numbers within the range of 12 to 42, 56 to 75 and 82, groups 2 to 14 of the periodic table Suspensions in which at least one selected from the group consisting of oxides containing at least one metal element belonging to the above and ultrafine particles of composite oxides are suspended, and metal copper fine particles or metal copper fine particles obtained by oxidizing the surface The mixture is heated while mixing, the medium of the suspension is removed, the ultrafine particles are adhered to the surface of the copper fine particles, and the copper fine particles adhering to the ultrafine particles collide with each other or with other objects. Thus, the ultrafine particles can be fixed to the surface of the copper fine particles.
[0028]
The metal copper fine particles used in the semi-dry support method or the metal copper fine particles obtained by oxidizing the surface, and the ultrafine particles of oxide and composite oxide may be the same as those used in the dry support method. The medium in which the ultrafine particles are suspended is not particularly limited, and generally water, acidic aqueous solution, basic aqueous solution, alcohol, organic solvent, or the like can be used. In this production method, a suspension having a predetermined solid content concentration may be prepared and used, or commercially available silica sol, alumina sol, titania sol, barium titanate sol, etc. may be used to dilute the concentration as necessary. You may adjust and use.
[0029]
Hereinafter, the present invention will be specifically described by way of examples, comparative examples, and production examples, but the present invention is not limited to such examples.
Examples 1-8
500 g of copper fine powder (Mitsui Mining & Smelting Co., Ltd. 1050Y, average primary particle size of about 0.5 μm), ultrafine alumina (Nippon Aerosil Co., Ltd., aluminum oxide C, average primary particle size 13 nm), silicon oxide (Japan) 300CF manufactured by Aerosil Co., Ltd., average primary particle size 7 nm), yttrium oxide (manufactured by CI Chemical Co., Ltd., average primary particle size 10 nm), magnesium oxide (100A manufactured by Ube Material Co., Ltd., average primary particle size 10 nm), barium titanate ( Prepared by sol-gel method using titanium propoxide and barium propoxide, average primary particle size 30 nm), or titanium oxide (P25 manufactured by Nippon Aerosil Co., Ltd., average primary particle size 13 nm), 25 g (copper fine powder) 5% by weight) or 5 g (1% by weight of the copper fine powder) was mixed with stirring for 15 minutes. As a result, copper fine particles having any of the above ultrafine particles adhered to the surface were obtained. Further, this was put into a hybridizer (manufactured by Nara Machinery Co., Ltd.) and circulated at 8000 rpm for 5 minutes to obtain a composite copper fine powder in which any one of the above ultrafine particles was fixed on the surface of the copper fine particles.
[0030]
In each of the obtained composite copper fine powders, each ultrafine particle was fixed on the surface of the metal copper fine particle, and therefore, even if the ultrafine particle was put in water and stirred, each ultrafine particle was not peeled off or floated (simply In the case of just stirring, each ultrafine particle floated and the water became cloudy). Further, as a result of SEM observation, it was confirmed that the composite copper fine powder to which each ultrafine particle was fixed had the ultrafine particles fixed uniformly on the surface and that the particle size was hardly changed.
[0031]
Using the thermomechanical analyzer (TMA / SS6000 manufactured by Seiko Denshi Kogyo Co., Ltd.), the composite copper fine powder obtained in the above Examples 1 to 8 was measured for the thermal contraction rate at a heating rate of 10 ° C./min. did. The results were as shown in Table 1.
As Comparative Example 1, the heat shrinkage rate was also measured in the same manner for untreated copper fine powder (1050Y manufactured by Mitsui Mining & Smelting Co., Ltd., average primary particle size: about 0.5 μm). The results are also shown in Table 1. In Comparative Example 1, since the melting of the copper fine powder started from the time when the temperature exceeded 900 ° C., the temperature increase was interrupted at that time, and the heat shrinkage rate was measured to be −15%.
[0032]
As is clear from the data in Table 1, the composite copper fine powders of the present invention of Examples 1 to 8 have a very small heat shrinkage rate at a high temperature as compared with the untreated copper fine powder of Comparative Example 1. It has become.
[0034]
Example 9
In place of the hybridizer (manufactured by Nara Machinery Co., Ltd.) used in Example 1, mechanofusion (manufactured by Hosokawa Micron) was used and the mixture was circulated at 3000 rpm for 30 minutes in the same manner as in Example 1, and the ultrafine alumina particles on the surface of the copper fine particles A composite copper fine powder to which was fixed was obtained.
[0035]
In the obtained composite copper fine powder, since the alumina ultrafine particles were fixed, the alumina ultrafine particles were not peeled off or floated even when the mixture was put into water and stirred. Further, as a result of SEM observation, it was confirmed that the composite copper fine powder to which the alumina ultrafine particles were fixed had the alumina ultrafine particles fixed uniformly on the surface and that the particle size was hardly changed.
[0036]
Examples 10-12
500 g of fine copper powder (Mitsui Mining & Smelting Co., Ltd., 1050Y, average primary particle size of about 0.5 μm), ultrafine strontium titanate (prepared by sol-gel method, average primary particle size of 10 nm), barium strontium titanate ( Ba 0.9 Sr 0.1 ) TiO 3 (prepared by sol-gel method, average primary particle size 10 nm) or calcium zirconia (prepared by sol-gel method using zirconium propoxide and dipropoxy calcium, average primary particle size 30 nm) 5 g (mixing ratio of 1% by weight with respect to copper fine powder) was stirred and mixed for 15 minutes. As a result, copper fine particles having any of the above ultrafine particles adhered to the surface were obtained. Further, this was put into a hybridizer (manufactured by Nara Machinery Co., Ltd.) and circulated at 8000 rpm for 5 minutes to obtain a composite copper fine powder in which any one of the above ultrafine particles was fixed on the surface of the copper fine particles.
[0037]
In each of the obtained composite copper fine powders, the ultrafine particles were fixed on the surface of the metal copper fine particles. Therefore, even if the ultrafine particles were put in water and stirred, the ultrafine particles did not peel or float. In addition, as a result of SEM observation, it was confirmed that the composite copper fine powder to which each ultrafine particle was fixed had the ultrafine particles fixed uniformly on the surface and that the particle size was hardly changed. Further, the composite copper fine powders of Examples 10 to 12 of the present invention exhibited substantially the same heat shrinkage rate as Example 7.
[0038]
Production Example 1
100 g of copper fine powder (1050Y manufactured by Mitsui Mining & Smelting Co., Ltd., average primary particle size of about 1 μm) was added to 1 liter of pure water and stirred to form a slurry. After stirring for 30 minutes, 100 g of hydrogen peroxide solution was added all at once. When the reaction was completed and no bubbles were generated, stirring was stopped, filtered, and dried to obtain fine copper powder having an oxidized surface. The average particle diameter (Ferret diameter) of the obtained copper fine particles by SEM observation was 1 μm.
[0045]
Example 13
To 2.5 liters of a solution obtained by diluting silica sol (manufactured by Nissan Chemical Co., Snowtex O, average primary particle size of about 10 nm) to 1/20 with water (silica content 10 g / l), copper fine powder (Mitsui Metal Mining) 500 g (manufactured by 1050Y Co., Ltd., average primary particle size of about 0.5 μm) was added and stirred well while heating. Moisture gradually evaporated and finally a dry powder was obtained. This was put into a hybridizer (manufactured by Nara Machinery Co., Ltd.) and circulated at 8000 rpm for 5 minutes to obtain a composite copper fine powder having silica ultrafine particles fixed on the surface of the copper fine particles.
[0046]
In the composite copper fine powder of the present invention obtained in Example 13 , as a result of SEM observation, it was confirmed that the silica ultrafine particles were uniformly fixed on the surface and that the particle size was hardly changed. . In each of the obtained composite copper fine powders, the ultrafine particles were fixed, so that the ultrafine particles were not peeled off or floated even if they were put into water and stirred. Moreover, each composite copper fine powder showed the thermal contraction rate similar to Examples 1-6, 8 according to the kind of metal oxide which has adhered.
[0047]
【The invention's effect】
As described above, the composite copper fine powder according to the present invention has a rapid thermal shrinkage start temperature shifted to around 1000 ° C., which is very suitable for use in forming an internal electrode of a multilayer capacitor. That is, it has a heat shrinkage characteristic close to the heat shrinkage curve of the ceramic substrate, and therefore, it is possible to prevent the occurrence of delamination and cracks in the production of large multilayer ceramic capacitors, and the thin ceramic dielectric and internal electrodes It is possible to manufacture a small multilayer multilayer ceramic capacitor made of the above without impairing dielectric properties and electrical properties. Further, by using a copper electrode material, a low inductance can be realized in high frequency applications that have been increasingly demanded in recent years.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15275599A JP4001438B2 (en) | 1999-05-31 | 1999-05-31 | Method for producing composite copper fine powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15275599A JP4001438B2 (en) | 1999-05-31 | 1999-05-31 | Method for producing composite copper fine powder |
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