JP2000345201A - Composite copper fine powder and method for producing the same - Google Patents
Composite copper fine powder and method for producing the sameInfo
- Publication number
- JP2000345201A JP2000345201A JP11152755A JP15275599A JP2000345201A JP 2000345201 A JP2000345201 A JP 2000345201A JP 11152755 A JP11152755 A JP 11152755A JP 15275599 A JP15275599 A JP 15275599A JP 2000345201 A JP2000345201 A JP 2000345201A
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- JP
- Japan
- Prior art keywords
- copper fine
- composite
- oxide
- metal
- fine particles
- 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.)
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- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Ceramic Capacitors (AREA)
Abstract
(57)【要約】
【課題】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、熱収縮特
性に優れている複合銅微粉末、そのような複合銅微粉末
の製造方法を提供すること。
【解決手段】金属銅微粒子表面に、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、及び
その製造方法。(57) Abstract: Composite copper fine powder having characteristics suitable for use as an internal electrode material of a multilayer ceramic capacitor, and particularly excellent in heat shrinkage properties, and such composite copper fine powder To provide a method for manufacturing the same. A composite copper fine powder in which at least one selected from the group consisting of an oxide containing at least one metal element and a composite oxide is fixed on the surface of metal copper fine particles, and a method for producing the same.
Description
【０００１】[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
銅微粉末及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer ceramic capacitor having characteristics suitable for use as an internal electrode material and an external electrode material of a multilayer ceramic capacitor. Delamination and cracks can be prevented in the production of
Also, the present invention relates to a fine composite copper powder capable of producing a small multilayer ceramic capacitor composed of a thin ceramic dielectric and internal electrodes without impairing the dielectric and electrical characteristics, and a method for producing the same.
【０００２】[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。2. Description of the Related Art A multilayer ceramic capacitor is obtained by alternately stacking ceramic dielectrics and internal electrodes in a layered form, pressing and firing, and integrating them by firing. The internal electrodes of such a multilayer ceramic capacitor are formed. In this case, a metal fine powder as an internal electrode material is made into a paste, printed on a ceramic base material using the paste, and a plurality of the printed base materials are laminated by heating and pressure bonding to be integrated. It is general to perform heating and firing in an atmosphere. Conventionally, platinum and palladium have been used as the internal electrode material. Recently, however, a technique using a base metal such as nickel or copper instead of a noble metal such as platinum or palladium has been developed and advanced.
【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。[0003] However, when metal copper fine powder is used, it tends to cause rapid thermal shrinkage at around 600 ° C, depending on its particle size. The firing temperature at the time of manufacturing a multilayer ceramic capacitor varies depending on the constituent components of the ceramic dielectric, and is based on a perovskite-type composite oxide such as BaTiO 3 or SrTiO 3 , to which a glass material is added. , Strontium, oxide powder such as calcium, etc., and lower the firing temperature to 1000 ° C.
Materials that can be sintered to a certain degree have also been developed.
【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。[0004] If the sintering temperature at the time of manufacturing a ceramic capacitor can be lowered, copper which is less expensive and has higher conductivity than nickel which has been used as an internal electrode material of a ceramic capacitor can be used. In addition, by using a copper electrode material, low inductance can be realized in high frequency applications, which have been increasingly required in recent years.
【０００５】[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。For the reasons described above, with respect to the copper fine powder for paste used in the production of the multilayer ceramic capacitor, in order to suppress delamination and cracking during firing, it is necessary to use copper fine particles. It is important to shift the rapid thermal shrinkage onset temperature to a higher temperature side to approximate the thermal shrinkage curve of the ceramic substrate.
【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
する複合銅微粉末を提供することを課題としている。ま
た、本発明はそのような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。The present invention has characteristics suitable for use as an internal electrode material of a multilayer ceramic capacitor,
In particular, it has a heat shrinkage characteristic close to the heat shrinkage curve of the ceramic substrate, and therefore can prevent delamination and cracks in the production of large multilayer ceramic capacitors. It is an object of the present invention to provide a fine composite copper powder capable of manufacturing a small-sized multilayer ceramic capacitor composed of the same without impairing the dielectric and electrical characteristics. Another object of the present invention is to provide a method for producing such a composite copper fine powder.
【０００７】[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。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, by fixing an oxide and / or composite oxide of a metal element on the surface of metal copper fine particles. The inventors have found that a composite copper fine powder having the above characteristics can be obtained, and that such a composite copper fine powder can be produced by any of a wet supporting method, a dry supporting method, and a semi-dry supporting method, and thus completed the present invention.
【０００８】即ち、本発明の複合銅微粉末は、金属銅微
粒子表面に、金属元素、好ましくは原子番号が１２〜４
２、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
していることを特徴とする。That is, the composite copper fine powder of the present invention has a metal element, preferably having an atomic number of 12 to 4
At least one selected from the group consisting of oxides and composite oxides containing at least one metal element belonging to Groups 2 to 14 of the periodic table in the range of 2, 56 to 75 and 82 is fixed. Features.
【０００９】また、本発明の複合銅微粉末の製造方法
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ることを特徴とする。The method for producing a composite copper fine powder according to the present invention is characterized in that a metal element, preferably having an atomic number of 12 to 12, is added to a slurry in which metal copper fine particles or metal copper fine particles whose surface is oxidized are dispersed in a 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 in the range of 42, 56 to 75 and 82 is added, and then the pH is adjusted with an acid or alkali. And fixing a metal oxide and / or a composite oxide derived from the water-soluble salt on the surface of the copper fine particles.
【００１０】更に、本発明の複合銅微粉末の製造方法
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１２〜４
２、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を特徴とする。Further, in the method for producing a composite copper fine powder of the present invention, the metal element, preferably having an atomic number of 12 to 4
Depositing at least one selected from the group consisting of oxides and composite oxide ultrafine particles containing at least one metal element belonging to Groups 2 to 14 of the periodic table within the range of 2, 56 to 75 and 82; The method is characterized in that the copper fine particles to which the ultrafine particles are adhered collide with each other or another object to fix the ultrafine particles on the surface of the copper fine particles.
【００１１】また、本発明の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
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
させることを特徴とする。The method for producing a composite copper fine powder according to the present invention is characterized in that the metal element, preferably, has an atomic number of 12 to 42 or 56.
A suspension in which at least one selected from the group consisting of oxides containing at least one metal element belonging to Groups 2 to 14 of the periodic table and ultrafine particles of composite oxides in the range of 75 to 82; The mixture is heated while mixing the liquid and the metallic copper fine particles or the metallic copper fine particles whose surface has been oxidized, the medium of the suspension is removed, and the ultrafine particles adhere to the surface of the copper fine particles. The ultrafine particles are fixed to the surface of the copper fine particles by colliding the copper fine particles adhered to each other or another object.
【００１２】[0012]
【発明の実施の形態】本発明の複合銅微粉末において
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。BEST MODE FOR CARRYING OUT THE INVENTION In the composite copper fine powder of the present invention, a metal element, preferably having an atomic number within the range of 12 to 42, 56 to 75 and 82, of 2 to 14 of the periodic table Since at least one selected from the group consisting of oxides and composite oxides containing at least one metal element belonging to the group III is fixed, the composite copper fine powder of the present invention is close to the heat shrinkage curve of the ceramic substrate. Since it has heat shrinkage characteristics, it is possible to prevent the occurrence of delamination and cracks in the production of large multilayer ceramic capacitors. In addition, it is possible to manufacture a small-sized multilayer ceramic capacitor composed of a thin ceramic dielectric and internal electrodes without impairing the dielectric and electrical characteristics.
【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。In order to manufacture a small multilayer ceramic capacitor without impairing the dielectric and electrical characteristics by using the paste containing the fine composite copper powder of the present invention for forming the internal electrodes, it is preferable to use atomic paste. Numbers 12 to 42, 56
A composite copper fine powder to which at least one selected from the group consisting of oxides and composite oxides containing at least one metal element belonging to Groups 2 to 14 of the periodic table in the range of 75 to 82 is fixed. Used, more preferably an atomic number of 12 to
42, 56 to 75 and 82 to 4 in the periodic table
A composite copper fine powder to which at least one selected from the group consisting of oxides and composite oxides containing at least one metal element belonging to Group 7, Group 7, Group 13 and Group 14 is used.
【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。A metal element belonging to Group 2 of the periodic table;
It is preferable to use a composite copper fine powder to which at least one selected from the group consisting of oxides of Y, Zr, Mn, Al, Si or lanthanoid elements is fixed. Further, as the above-mentioned complex oxide, various compounds including the complex oxide described below can be used. 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 on the surface of the copper fine particles. Preferably, there is.
【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Ｚ
ｒ、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。[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 Where X is Sr, Ca, Mg or Pb, and Z is Z
r, Y, Sn or Ge, m is a value in the range of 0 to 1, and n is a value in the range of 0 to 1. It is preferable that at least one selected from the group consisting of the composite oxides represented by the formula (1) is fixed, and those composite oxides can be fixed alone or in combination of two or more. Alternatively, the composite oxide may be used as a main component, and at least one of the above-mentioned various oxides may be used as an additive component to fix the composite oxide.
【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、Ａｌ
2 Ｏ3 、Ｇａ2 Ｏ3 、Ｙ2 Ｏ3 、ＳｉＯ2 、ＴｉＯ2 、
ＺｒＯ2 、Ｃｒ2 Ｏ3 、ＭｎＯ2 、Ｍｎ3 Ｏ4 、Ｎｂ2
Ｏ5 、ＢａＴｉＯ3 、ＣａＴｉＯ3 、ＳｒＴｉＯ3 、Ｂ
ａＺｒＯ3 、ＣａＺｒＯ3 、ＳｒＺｒＯ3 、（Ｍｇ，Ｃ
ａ）ＴｉＯ3 、（Ｂａ，Ｃａ）（Ｔｉ，Ｚｒ）Ｏ3 、Ｐ
ｂＴｉＯ3 、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3 、（Ｐｂ，Ｃａ）
ＴｉＯ3 、ＭｇＡｌ2 Ｏ4 、ＢａＴｉ4 Ｏ9 、Ｎｄ2 Ｏ
3 、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。The above oxides and composite oxides include, for example, MgO, CaO, SrO, BaO, ZnO, AlO
2 O 3 , Ga 2 O 3 , Y 2 O 3 , SiO 2 , TiO 2 ,
ZrO 2 , Cr 2 O 3 , MnO 2 , Mn 3 O 4 , Nb 2
O 5 , BaTiO 3 , CaTiO 3 , SrTiO 3 , B
aZrO 3 , CaZrO 3 , SrZrO 3 , (Mg, C
a) TiO 3 , (Ba, Ca) (Ti, Zr) O 3 , P
bTiO 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, and they can also be used as a mixture. Further, these oxides and / or composite oxides may be doped with a metal oxide such as Nb, W, La, Y, and Mo.
【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。In the composite copper fine powder of the present invention, when the composite copper fine powder is used as a paste for forming an internal electrode of a multilayer ceramic capacitor, it is desirable that the finer powder is capable of forming a fine electrode. The average particle diameter of the copper fine powder by SEM observation is preferably 3 μm or less, more preferably 1 μm or less. In general, as the metal fine powder becomes finer, the heat shrinkage is more likely to occur.However, in the composite copper fine powder of the present invention, the effect of preventing heat shrinkage is exhibited even when the metal fine powder becomes finer. It becomes more and more prominent.
【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。The total amount of the at least one kind selected from the group consisting of these oxides and composite oxides is preferably 0.05 to 15% by weight based on the weight of the copper fine powder.
More preferably 0.5 to 13% by weight, even more preferably 1 to 13% by weight.
-10% by weight. When the total fixing amount is less than 0.05% by weight, the effect achieved by fixing the oxide and / or the composite oxide tends to be insufficient.
When the amount exceeds about 10% by weight, when such a composite copper fine powder is used as an internal electrode material of a multilayer ceramic capacitor, the dielectric properties of the capacitor tend to be adversely affected.
【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。The copper fine particles or the copper fine particles whose surface is oxidized for use in the method for producing a composite copper fine powder of the present invention can be prepared by any of mechanical pulverization, atomization, electrolytic deposition, evaporation, wet reduction and the like. It may be obtained by the method.
When the composite copper fine powder of the present invention is used for a paste for forming an internal electrode of a multilayer ceramic capacitor, the average particle diameter of the copper fine particles used for the production is preferably 3 μm or less, more preferably 1 μm or less. preferable.
【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る。The composite copper fine powder of the present invention is prepared by a semi-dry supporting method in which an aqueous suspension of a metal oxide or an ultrafine particle of a composite oxide is supported on fine metal copper particles and dried by a wet supporting method or a dry supporting method. Can be manufactured by In the method for producing a composite copper fine powder of the present invention when carried out according to the wet supporting method, a metal element, preferably an atom, is added to a slurry in which metal copper fine particles or metal copper fine particles having an oxidized surface are dispersed in a liquid. Number is 12-42, 56-75
And 82, 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 is added, and then the pH is adjusted with an acid or alkali.
To fix the metal oxide and / or composite oxide derived from the water-soluble salt on the surface of the copper fine particles.
【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。The above-mentioned water-soluble salt used in the method for producing a composite copper fine powder of the present invention when carried out according to the wet supporting method is water-soluble, but may be one which can be converted into a water-insoluble oxide or composite oxide. It is not particularly limited. For example, halides, nitrates, sulfates, oxalates, oxides, and alkali metal salts such as aluminate and silicic acid of these metal elements can be used.
【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（Ａ
ｌ2 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。In the method for producing a composite copper fine powder of the present invention when carried out according to the wet supporting method, whether an acid or an alkali is used to adjust the pH varies depending on the kind of the water-soluble salt. However, the type of acid or alkali used is not particularly limited. For example, when an oxide in parentheses is produced using the following water-soluble salts, an aqueous sodium hydroxide solution can be used. Titanium sulfate (TiO 2 ), manganese sulfate (MnO 2 ), chromium chloride (Cr 2 O 3 ), yttrium chloride (Y 2 O 3 ),
Zirconium chloride oxide (ZrO 2 ). In addition, when an oxide in parentheses is formed using the following water-soluble salt, dilute sulfuric acid can be used. Sodium aluminate (A
l 2 O 3 ), sodium silicate (SiO 2 ). By adjusting the pH as described above, the water-soluble salt is converted into an oxide or a composite oxide, deposited on the surface of the copper fine particles, and fixed to become the composite copper fine powder of the present invention.
【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は、上記の処理工程及びその
後の洗浄、乾燥工程で構成されていてもよいが、上記の
湿式担持法により銅微粒子表面に上記の水溶性塩から誘
導される金属酸化物及び／又は複合酸化物を固着させ、
洗浄し、乾燥させた後、追加の工程として、該酸化物及
び／又は複合酸化物の固着している銅微粒子を、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、相互に又
は他物体と衝突させて該銅微粒子の表面とその表面に存
在する酸化物及び／又は複合酸化物との固着強度を更に
改善することができる。The method for producing the composite copper fine powder of the present invention when carried out according to the wet loading method may comprise the above-mentioned treatment step and subsequent washing and drying steps. A metal oxide and / or a composite oxide derived from the water-soluble salt is fixed on the surface of the fine particles,
After washing and drying, as an additional step, the copper fine particles to which the oxide and / or the composite oxide are fixed are removed, for example, by using an angmill, a hybridizer, a mechanofusion, a coatmizer, a dispercoat, or a jetmizer. By treating with any of the devices, it is possible to further improve the bonding strength between the surface of the copper fine particles and the oxide and / or composite oxide present on the surface by colliding with each other or another object.
【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。In the method for producing a composite copper fine powder of the present invention when carried out according to the dry loading method, a metal element, preferably an atomic number of 12 to At least one selected from the group consisting of oxides containing at least one metal element belonging to Groups 2 to 14 of the periodic table and ultrafine particles of composite oxides in the range of 42, 56 to 75 and 82; The ultrafine particles can be fixed to the surface of the copper fine particles by colliding the copper fine particles with the ultrafine particles with each other or with another object.
【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、０．０
５μｍ以下であることが最も好ましい。The metal copper fine particles or the metal copper fine particles whose surface has been subjected to oxidation treatment used in the method for producing the composite copper fine powder of the present invention when the method is carried out according to the dry loading method are the same as those of the present invention. When used as a paste for forming electrodes, the average particle size is 3 μm.
Or less, more preferably 1 μm or less. In addition, oxides, ultrafine particles of composite oxide,
Since the smaller the particle size, the smaller the amount, the more it can be fixed uniformly, the average particle size is preferably 0.5 μm or less, more preferably 0.1 μm or less, and 0.07 μm or less.
Most preferably, it is 5 μm or less.
【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。As a method for fixing ultrafine particles of an oxide or a composite oxide to the surface of metal copper fine particles or metal copper fine particles whose surface has been subjected to oxidation treatment, the metal copper fine particles and the ultrafine particles of the oxide or composite oxide are used. , And then the copper fine particles to which the ultra fine particles are adhered are caused to collide with each other or another object to fix the ultra fine particles on the surface of the copper fine particles. Other methods include charging the copper fine particles and the ultrafine particles of the oxide or composite oxide into an apparatus such as an angmill, hybridizer, mechanofusion, coatmizer, dispercoat, jetmizer, and mixing and fixing. Can also be performed simultaneously.
【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。In the method for producing a composite copper fine powder according to the present invention when carried out according to the semi-dry loading method, the metal element, preferably having an atomic number within the range of 12 to 42, 56 to 75 and 82, of the periodic table is used. A suspension in which at least one selected from the group consisting of oxides containing at least one metal element belonging to Groups 14 to 14 and ultrafine particles of composite oxides, and metal copper fine particles or a surface thereof were oxidized. Heat while mixing with metallic copper fine particles, remove the medium of the suspension,
The ultrafine particles can be adhered to the surface of the copper fine particles, and the copper fine particles to which the ultrafine particles are adhered can collide with each other or another object to fix the ultrafine particles on the surface of the copper fine particles.
【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。The metal copper fine particles or metal copper fine particles whose surface is oxidized, and the oxide and composite oxide ultrafine particles used in the above-mentioned semi-dry loading method may be the same as those used in the above-mentioned dry loading method. The medium in which the ultrafine particles are suspended is not particularly limited, and generally, water, an acidic aqueous solution, a basic aqueous solution, an alcohol, an organic solvent, or the like can be used.
In this production method, even if a suspension having a predetermined solid content is prepared and used, or a commercially available silica sol, alumina sol, titania sol, barium titanate sol, or the like is used,
If necessary, the concentration may be adjusted by dilution or the like before use.
【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３００Ｃ
Ｆ、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１０ｎ
ｍ）、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。Hereinafter, the present invention will be described specifically with reference to Examples, Comparative Examples, and Production Examples, but the present invention is not limited to such cases. Examples 1 to 8 Copper fine powder (1050Y, manufactured by Mitsui Kinzoku Mining Co., Ltd., average 1)
500 g, ultrafine alumina (aluminum oxide C manufactured by Nippon Aerosil Co., Ltd., average primary particle size 13 nm), silicon oxide (300 C manufactured by Nippon Aerosil Co., Ltd.)
F, average primary particle diameter 7 nm), yttrium oxide (C-I Kasei Co., Ltd., average primary particle diameter 10 nm), magnesium oxide (Ube Material 100A, average primary particle diameter 10 n)
m), barium titanate (prepared by a 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) Either 25g (5% by weight based on copper fine powder) or 5g
(A mixing ratio of 1% by weight with respect to the 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 is put into a hybridizer (manufactured by Nara Machinery Co., Ltd.), and 8000 rpm
For 5 minutes to obtain a composite copper fine powder having any one of the above ultrafine particles fixed on the surface of the copper fine particles.
【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。In each obtained composite copper fine powder,
Since each ultrafine particle is fixed on the surface of the metallic copper fine particle,
Each ultrafine particle did not separate or float even when it was thrown into water and stirred (when only agitated, each ultrafine particle floated and the water became cloudy). The composite copper fine powder to which the ultrafine particles were fixed was observed by SEM, and it was confirmed that the ultrafine particles were uniformly fixed to the surface and that the particle size was hardly changed.
【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／ＳＳ
６０００）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９０
０℃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。The composite copper fine powder obtained in the above Examples 1 to 8 was subjected to a thermomechanical analyzer (TMA / SS manufactured by Seiko Denshi Kogyo).
6000) in a nitrogen gas atmosphere at a heating rate of 10 ° C.
The heat shrinkage was measured at / min. The results are as shown in Table 1. The heat shrinkage of untreated copper fine powder (1050Y, manufactured by Mitsui Mining & Smelting Co., Ltd., average primary particle size: about 0.5 μm) was measured in the same manner as Comparative Example 1. The results are also shown in Table 1. In Comparative Example 1, 90
Since the melting of the copper fine powder started from the point where the temperature exceeded 0 ° C., the heating was interrupted at that point, and the heat shrinkage was measured.
15%.
【００３２】 [0032]
【００３３】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。As is clear from the data in Table 1, the composite copper fine powder of the present invention of Examples 1 to 8 has a higher heat shrinkage at high temperature than the untreated copper fine powder of Comparative Example 1. Is extremely small.
【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。Example 9 Copper was used in the same manner as in Example 1 except that the hybridizer (manufactured by Nara Kikai Seisakusho) used in Example 1 was replaced with mechanofusion (manufactured by Hosokawa Micron) and circulated at 3000 rpm for 30 minutes. A composite copper fine powder having ultrafine alumina particles fixed to the surface of the fine particles was obtained.
【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。In the obtained composite copper fine powder, alumina ultrafine particles were fixed, so that even if the particles were put into water and stirred, the alumina ultrafine particles did not peel or float. Further, as a result of SEM observation, it was confirmed that the ultrafine alumina particles were uniformly fixed on the surface of the composite copper fine powder to which the ultrafine alumina particles were fixed, and the particle diameter was hardly changed.
【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（Ba0.9S
r0.1)TiO3 （ゾルゲル法によって調製、平均１次粒径１
０ｎｍ）、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、８
０００ｒｐｍ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。Examples 10 to 12 Copper fine powder (1050Y manufactured by Mitsui Kinzoku Mining Co., Ltd., average 1)
500 g, ultrafine strontium titanate (prepared by a sol-gel method, average primary particle size 10 nm), barium strontium titanate (Ba 0.9 S
r 0.1 ) TiO 3 (prepared by sol-gel method, average primary particle size 1
0 nm) or calcium zirconate (prepared by a sol-gel method using zirconium propoxide and dipropoxy calcium, average primary particle diameter: 30 nm) (15% by weight with respect to copper fine powder). Stir and mix for 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 8
The mixture was circulated at 000 rpm for 5 minutes to obtain a fine composite copper powder in which any of the above ultrafine particles was fixed on the surface of the copper fine particles.
【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。In each of the obtained composite copper fine powders,
Since each ultrafine particle is fixed on the surface of the metallic copper fine particle,
Each ultrafine particle did not exfoliate or float even when put into water and stirred. In addition, as a result of SEM observation, it was confirmed that the ultrafine particles were fixed uniformly on the surface of the composite copper fine powder to which the ultrafine particles were fixed, and that the particle size was hardly changed. Further, the composite copper fine powders of Examples 10 to 12 of the present invention showed almost the same heat shrinkage as that of Example 7.
【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。Production Example 1 Copper fine powder (1050Y manufactured by Mitsui Kinzoku Mining Co., Ltd., average 1)
100 g of the next particle size (about 1 μm) in 1 liter of pure water.
The mixture was 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, and the mixture was filtered and dried to obtain a fine copper powder whose surface was oxidized. The average particle diameter (Ferre diameter) of the obtained copper fine particles by SEM observation was 1 μm.
【００３９】実施例１３ 製造例１で製造した表面酸化処理銅微粉末１００ｇを純
水１リットル中に加え、攪拌してスラリー化し、６０℃
に加熱し、この温度に保持した。該スラリーに硫酸チタ
ン（Ｔｉ：５重量％品）１９．２ｇを一括添加し、水酸
化ナトリウム水溶液（ＮａＯＨ：１Ｎ）を添加してｐＨ
を８に調整した。そのまま１時間攪拌した後、濾過し、
乾燥してＴｉＯ2 が固着している複合銅微粉末を得た。Example 13 100 g of the surface-oxidized copper fine powder produced in Production Example 1 was added to 1 liter of pure water, and the mixture was stirred to form a slurry.
And kept at this temperature. To the slurry, 19.2 g of titanium sulfate (Ti: 5% by weight) was added all at once, and an aqueous solution of sodium hydroxide (NaOH: 1N) was added to adjust the pH.
Was adjusted to 8. After stirring as it is for 1 hour, it was filtered,
After drying, a composite copper fine powder having TiO 2 fixed thereto was obtained.
【００４０】実施例１４ 製造例１で製造した表面酸化処理銅微粉末１００ｇを純
水１リットル中に加え、攪拌してスラリー化し、６０℃
に加熱し、この温度に保持した。次いで該スラリーに、
ケイ酸ナトリウム（水ガラス）６．５ｇを６０ｍｌの純
水に溶解した水溶液を一括添加し、希硫酸を添加してｐ
Ｈを６に調整した。そのまま１時間攪拌した後、濾過
し、乾燥してＳｉＯ2 が固着している複合銅微粉末を得
た。Example 14 100 g of the surface-oxidized copper fine powder produced in Production Example 1 was added to 1 liter of pure water, and stirred to form a slurry.
And kept at this temperature. Then the slurry
An aqueous solution in which 6.5 g of sodium silicate (water glass) is dissolved in 60 ml of pure water is added all at once, and dilute sulfuric acid is added to add p.
H was adjusted to 6. After stirring for 1 hour as it was, the mixture was filtered and dried to obtain a fine composite copper powder to which SiO 2 was fixed.
【００４１】実施例１５ 製造例１で製造した表面酸化処理銅微粉末１００ｇを純
水１リットル中に加え、攪拌してスラリー化し、６０℃
に加熱し、この温度に保持した。該スラリーに、塩化イ
ットリウム３．５ｇを５０ｍｌの純水に溶解した水溶液
を一括添加し、水酸化ナトリウム水溶液（ＮａＯＨ：１
Ｎ）を添加してｐＨを６に調整した。そのまま１時間攪
拌した後、濾過し、乾燥してＹ2 Ｏ3 が固着している複
合銅微粉末を得た。Example 15 100 g of the surface-oxidized copper fine powder produced in Production Example 1 was added to 1 liter of pure water, and the mixture was stirred to form a slurry.
And kept at this temperature. An aqueous solution in which 3.5 g of yttrium chloride was dissolved in 50 ml of pure water was added to the slurry at once, and an aqueous sodium hydroxide solution (NaOH: 1) was added.
N) was added to adjust the pH to 6. After stirring for 1 hour as it was, the mixture was filtered and dried to obtain a fine composite copper powder to which Y 2 O 3 was fixed.
【００４２】実施例１６ 製造例１で製造した表面酸化処理銅微粉末１００ｇを純
水１リットル中に加え、攪拌してスラリー化し、６０℃
に加熱し、この温度に保持した。該スラリーに、塩化酸
化ジルコニウム３．５ｇを５０ｍｌの純水に溶解した水
溶液を一括添加し、水酸化ナトリウム水溶液（ＮａＯ
Ｈ：１Ｎ）を添加してｐＨを６に調整した。そのまま１
時間攪拌した後、濾過し、乾燥してＺｒＯ2 が固着して
いる複合銅微粉末を得た。Example 16 100 g of the surface-oxidized copper fine powder produced in Production Example 1 was added to 1 liter of pure water, and the mixture was stirred to form a slurry.
And kept at this temperature. To the slurry, an aqueous solution in which 3.5 g of zirconium chloride chloride was dissolved in 50 ml of pure water was added all at once, and an aqueous sodium hydroxide solution (NaO
H: 1N) was added to adjust the pH to 6. 1 as it is
After stirring for an hour, the mixture was filtered and dried to obtain a fine composite copper powder to which ZrO 2 was fixed.
【００４３】実施例１７ 製造例１で製造した表面酸化処理銅微粉末１００ｇを純
水１リットル中に加え、攪拌してスラリー化し、６０℃
に加熱し、この温度に保持した。該スラリーに、硫酸マ
ンガン１５．７ｇを１００ｍｌの純水に溶解した水溶液
を一括添加し、水酸化ナトリウム水溶液（ＮａＯＨ：１
Ｎ）を添加してｐＨを８に調整した。そのまま１時間攪
拌した後、濾過、乾燥してＭｎＯ2 が固着している複合
銅微粉末を得た。Example 17 100 g of the surface-oxidized copper fine powder produced in Production Example 1 was added to 1 liter of pure water, and the mixture was stirred to form a slurry.
And kept at this temperature. To the slurry, an aqueous solution in which 15.7 g of manganese sulfate was dissolved in 100 ml of pure water was added all at once, and an aqueous sodium hydroxide solution (NaOH: 1
N) was added to adjust the pH to 8. After stirring for 1 hour as it was, the mixture was filtered and dried to obtain a fine composite copper powder to which MnO 2 was fixed.
【００４４】実施例１８ 製造例１で製造した表面酸化処理銅微粉末１００ｇを純
水１リットル中に加え、攪拌してスラリー化し、６０℃
に加熱し、この温度に保持した。該スラリーに、アルミ
ン酸ナトリウム５．５ｇを１００ｍｌの純水に溶解した
水溶液を一括添加し、希硫酸を添加してｐＨを８に調整
した。そのまま１時間攪拌した後、濾過し、乾燥してＡ
ｌ2 Ｏ3 が固着している複合銅微粉末を得た。Example 18 100 g of the surface-oxidized copper fine powder produced in Production Example 1 was added to 1 liter of pure water, and the mixture was stirred to form a slurry.
And kept at this temperature. An aqueous solution in which 5.5 g of sodium aluminate was dissolved in 100 ml of pure water was added to the slurry at a time, and the pH was adjusted to 8 by adding dilute sulfuric acid. The mixture was stirred for 1 hour, filtered, dried and dried.
A composite copper fine powder to which l 2 O 3 was fixed was obtained.
【００４５】実施例１９ 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。Example 19 Silica sol (Snowtex O, manufactured by Nissan Chemical Industries, average 1)
2.5 liters of a solution (silica content: 10 g / l) obtained by diluting the primary particle size (approximately 10 nm) to 1/20 with water, and adding copper fine powder (1050Y, manufactured by Mitsui Kinzoku Mining Co., Ltd., average primary particle size: approx. (5 μm), 500 g, and stirred well while heating. The water evaporates slowly and finally a dry powder is obtained.
This was charged into a hybridizer (manufactured by Nara Machinery Co., Ltd.) and circulated at 8,000 rpm for 5 minutes to obtain a composite copper fine powder having ultrafine silica particles fixed to the surface of the copper fine particles.
【００４６】実施例１３〜１９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。In the composite copper fine powder of the present invention obtained in Examples 13 to 19, as a result of SEM observation, ultrafine silica particles were uniformly fixed on the surface, and the particle size was hardly changed. It was confirmed that. Since the ultrafine particles were fixed in each of the obtained composite copper fine powders, the ultrafine particles did not peel off or float even when they were put into water and stirred. Further, each composite copper fine powder showed a heat shrinkage similar to that of Examples 1 to 6 and 8, depending on the type of the metal oxide fixed thereto.
【００４７】[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。As described above, the composite copper fine powder according to the present invention has a sharp thermal shrinkage onset temperature shifted to around 1000 ° C., and is extremely suitable for use in forming internal electrodes of a multilayer capacitor. That is, it has a heat shrinkage characteristic close to the heat shrinkage curve of the ceramic base material, so that it is possible to prevent the occurrence of delamination and cracks in the production of large-sized multilayer ceramic capacitors, and to reduce the thickness of the ceramic dielectric and the internal electrodes. Can be manufactured without deteriorating the dielectric and electrical characteristics. In addition, by using a copper electrode material, low inductance can be realized in high frequency applications, which have been increasingly required in recent years.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4K017 AA06 BA05 BB01 BB09 BB11 BB12 BB16 DA01 EA02 4K018 BA02 BB04 BC15 BC18 BC28 BD04 KA33 5E001 AA01 AB03 AC09 AE01 AE02 AE03 AH01 AJ01 5E082 AB03 BC33 EE04 EE26 EE27 EE35 EE45 FF05 FG06 FG26 FG46 PP03 PP09 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4K017 AA06 BA05 BB01 BB09 BB11 BB12 BB16 DA01 EA02 4K018 BA02 BB04 BC15 BC18 BC28 BD04 KA33 5E001 AA01 AB03 AC09 AE01 AE02 AE03 AH01 AJ01 5E082 AB03 EE27 EE26 EE04 EE26 FG46 PP03 PP09
Claims (18)
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種が固着していることを特徴とする複
合銅微粉末。A composite copper fine powder characterized in that at least one selected from the group consisting of an oxide containing at least one metal element and a composite oxide is fixed on the surface of metal copper fine particles.
〜４２、５６〜７５及び８２の範囲内で周期表の２〜１
４族に属する金属元素の少なくとも１種を含む酸化物及
び複合酸化物であることを特徴とする請求項１記載の複
合銅微粉末。2. An oxide and a composite oxide having an atomic number of 12
~ 42, 56 ~ 75 and 82 in the periodic table within the range of
2. The composite copper fine powder according to claim 1, wherein the composite copper oxide is an oxide and a composite oxide containing at least one metal element belonging to Group IV.
〜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であることを特徴
とする請求項２記載の複合銅微粉末。3. An oxide and a composite oxide having an atomic number of 12
2 to 4 of the periodic table within the range of ~ 42, 56 to 75 and 82
The composite copper fine powder according to claim 2, which is an oxide or a composite oxide containing at least one metal element belonging to Group 7, Group 7, Group 13, or Group 14.
素、Ｙ、Ｚｒ、Ｍｎ、Ａｌ、Ｓｉ又はランタノイド元素
の酸化物であることを特徴とする請求項３記載の複合銅
微粉末。4. The fine composite copper powder according to claim 3, wherein the oxide is an oxide of a metal element belonging to Group 2 of the periodic table, Y, Zr, Mn, Al, Si or a lanthanoid element. .
電体と同一組成の複合酸化物であることを特徴とする請
求項１記載の複合銅微粉末。5. The composite copper fine powder according to claim 1, wherein the composite oxide is a composite oxide having the same composition as a dielectric of the ceramic capacitor.
ｒ、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
複合酸化物であることを特徴とする請求項１記載の複合
銅微粉末。6. The composite oxide has 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 Z
r, Y, Sn or Ge, m is a value in the range of 0 to 1, and n is a value in the range of 0 to 1. The composite copper fine powder according to claim 1, which is a composite oxide represented by the following formula:
酸化物からなる群より選ばれる少なくとも１種、及請求
項１〜４の何れかに記載の酸化物からなる群より選ばれ
る少なくとも１種が固着していることを特徴とする請求
項１記載の複合銅微粉末。7. At least one selected from the group consisting of the composite oxide according to claim 6 and at least one selected from the group consisting of the oxide according to any one of claims 1 to 4 on the surface of the metal copper fine particles. The composite copper fine powder according to claim 1, wherein one kind is fixed.
ることを特徴とする請求項１〜７の何れかに記載の複合
銅微粉末。8. The composite copper fine powder according to claim 1, wherein the average particle size of the metal copper fine particles is 3 μm or less.
れる少なくとも１種の合計固着量が金属銅微粒子の重量
に対して０．０５〜１５重量％であることを特徴とする
請求項１〜８の何れかに記載の複合銅微粉末。9. The method according to claim 1, wherein the total fixing amount of at least one selected from the group consisting of oxides and composite oxides is 0.05 to 15% by weight based on the weight of the metallic copper fine particles. 9. The composite copper fine powder according to any one of items 1 to 8.
粉末からなる、セラミックコンデンサ用電極材料。10. An electrode material for a ceramic capacitor, comprising the composite copper fine powder according to any one of claims 1 to 9.
ある、請求項１０記載のセラミックコンデンサ用電極材
料。11. The electrode material for a ceramic capacitor according to claim 10, which is an internal electrode material for a ceramic capacitor.
ある、請求項１０記載のセラミックコンデンサ用電極材
料。12. The electrode material for a ceramic capacitor according to claim 10, which is an external electrode material for a ceramic capacitor.
属銅微粒子が液中に分散しているスラリーに、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ることを特
徴とする複合銅微粉末の製造方法。13. An aqueous solution containing at least one selected from the group consisting of water-soluble salts of metal elements is added to a slurry in which metal copper fine particles or metal copper fine particles whose surfaces have been oxidized are dispersed in a liquid, Then, the pH is adjusted with an acid or an alkali, and the metal oxide derived from the water-soluble salt and / or
Alternatively, a method for producing a composite copper fine powder, comprising fixing a composite oxide to the surface of the copper fine particles.
属銅微粒子が液中に分散しているスラリーに、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請求項１３記
載の複合銅微粉末の製造方法。14. An aqueous solution containing at least one selected from the group consisting of a water-soluble salt of a metal element is added to a slurry in which metal copper fine particles or metal copper fine particles whose surface has been oxidized are dispersed in a liquid, Then, the pH is adjusted with an acid or an alkali, and the metal oxide derived from the water-soluble salt and / or
Or fix the composite oxide on the surface of the copper fine particles, washed,
After drying, the obtained copper oxide particles to which the obtained metal oxide and / or composite oxide are fixed are caused to collide with each other or another object, and the surface of the copper fine particles and the metal oxide and / or the composite oxide are The method for producing a composite copper fine powder according to claim 13, wherein the adhesion of the composite copper powder is enhanced.
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を用いて、金属酸化物
及び／又は複合酸化物が固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
徴とする請求項１４記載の複合銅微粉末の製造方法。15. The method according to claim 15, wherein the copper fine particles to which the metal oxide and / or the composite oxide are adhered to each other or each other by using any one of an ongmill, a hybridizer, a mechanofusion, a coatmizer, a dispercoat, and a jetmizer. The method for producing a composite copper fine powder according to claim 14, wherein the adhesion of the metal oxide and / or the composite oxide to the surface of the copper fine particles is enhanced by colliding with another object.
属銅微粒子の表面に、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を特徴とする複合
銅微粉末の製造方法。16. At least one selected from the group consisting of oxides containing at least one metal element and ultrafine particles of composite oxides is adhered to the surfaces of the metal copper fine particles or the metal copper fine particles whose surfaces have been oxidized. A method of producing a composite copper fine powder, wherein the ultrafine particles adhere to the surface of the fine copper particles by colliding the ultrafine particles with each other or another object.
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を特徴とする複合銅微粉末
の製造方法。17. A suspension in which at least one selected from the group consisting of an oxide containing at least one metal element and ultrafine particles of a composite oxide is suspended, and the metal copper fine particles or the surface are oxidized. The mixture is heated while mixing with the metallic copper fine particles, 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 to which the ultrafine particles are adhered to each other or other particles. A method for producing a fine composite copper powder, wherein the ultrafine particles are fixed to the surface of the copper fine particles by colliding with an object.
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を用いて、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
とする請求項１６又は１７記載の複合銅の製造方法。18. The copper fine particles to which ultrafine particles are adhered to each other or another object by using any one of an ongmill, a hybridizer, a mechanofusion, a coatmizer, a dispercoat, and a jetmizer. The method for producing composite copper according to claim 16 or 17, wherein the ultrafine particles are fixed to the surface of the copper fine particles.
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 |
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| 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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| Publication Number | Publication Date |
|---|---|
| JP2000345201A true JP2000345201A (en) | 2000-12-12 |
| JP4001438B2 JP4001438B2 (en) | 2007-10-31 |
Family
ID=15547464
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15275599A Expired - Lifetime JP4001438B2 (en) | 1999-05-31 | 1999-05-31 | Method for producing composite copper fine powder |
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| Country | Link |
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