JP2018070951A - Powder for conductive paste and production method of conductive layer - Google Patents
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本発明は、導電ペースト用粉末、および導電層の製造方法に関する。 The present invention relates to a conductive paste powder and a method for producing a conductive layer.
金属ニッケル粉末は、導電ペースト用粉末として使用されている。導電ペーストは、金属ニッケル粉末の他に、バインダーや有機溶剤を含む。導電ペーストは、分散剤をさらに含んでもよい。導電ペーストは、バインダーや有機溶剤、分散剤を分解、揮発させる脱バインダー処理の後、還元雰囲気下で熱処理され、内部電極層や外部電極層、電気回路層などの導電層を形成する。導電ペーストは、多層セラミック回路基板や積層セラミックコンデンサなどの製造に用いられる。 Metallic nickel powder is used as a conductive paste powder. The conductive paste contains a binder and an organic solvent in addition to the metallic nickel powder. The conductive paste may further contain a dispersant. The conductive paste is heat-treated in a reducing atmosphere after debinding to decompose and volatilize the binder, organic solvent, and dispersant, and forms conductive layers such as internal electrode layers, external electrode layers, and electric circuit layers. The conductive paste is used for manufacturing a multilayer ceramic circuit board, a multilayer ceramic capacitor, and the like.
例えば、積層セラミックコンデンサは、誘電体グリーンシート上に導電ペーストをスクリーン印刷したものを複数枚重ねて熱圧着し、脱バインダー処理の後、還元雰囲気下で熱処理して製造される。積層セラミックコンデンサは、誘電体グリーンシートを焼成してなる誘電体層と、導電ペーストの塗布層を焼成してなる内部電極層とを交互に重ねた構造を有する。 For example, a multilayer ceramic capacitor is manufactured by stacking a plurality of screen-printed conductive pastes on a dielectric green sheet, thermocompression bonding, debinding, and then heat-treating in a reducing atmosphere. The multilayer ceramic capacitor has a structure in which dielectric layers formed by firing a dielectric green sheet and internal electrode layers formed by firing a coating layer of a conductive paste are alternately stacked.
内部電極層などの導電層の導電率を高めるため、導電ペーストに含まれる金属ニッケル粉末が熱処理によって連続的につながることが求められる。 In order to increase the conductivity of the conductive layer such as the internal electrode layer, it is required that the metallic nickel powder contained in the conductive paste is continuously connected by heat treatment.
しかしながら、金属ニッケル粉末が熱処理によって連続的につながるとき、熱収縮が生じる。熱収縮が大き過ぎると、クラックや変形などが生じ、導電層の性能が劣化する。 However, thermal shrinkage occurs when the metallic nickel powder is continuously connected by heat treatment. If the thermal shrinkage is too large, cracks and deformations occur, and the performance of the conductive layer deteriorates.
そこで、特許文献１の実施例では、導電性や熱収縮特性を改善するため、金属ニッケル微粒子表面に酸化ジルコニウムまたはチタン酸ストロンチウムが固着しており、さらにその表面に不飽和脂肪酸が担持されている複合ニッケル微粉末が提案されている。 Therefore, in the example of Patent Document 1, zirconium oxide or strontium titanate is fixed to the surface of the metal nickel fine particles in order to improve conductivity and heat shrinkage characteristics, and an unsaturated fatty acid is supported on the surface. Composite nickel fine powder has been proposed.
従来から、熱処理後の導電性や熱収縮特性を改善するための技術が提案されているが、より熱処理後の導電性や熱収縮特性を改善できる技術が望まれていた。 Conventionally, techniques for improving the conductivity and heat shrinkage characteristics after heat treatment have been proposed, but a technique that can further improve the conductivity and heat shrinkage characteristics after heat treatment has been desired.
本発明は、上記課題に鑑みてなされたものであって、熱処理後の導電性、および熱収縮特性を改善できる、導電ペースト用粉末の提供を主な目的とする。 This invention is made | formed in view of the said subject, Comprising: It aims at provision of the powder for electrically conductive pastes which can improve the electroconductivity after heat processing and a heat contraction characteristic.
上記課題を解決するため、本発明の一態様によれば、
金属ニッケル粉末と、
前記金属ニッケル粉末と混在する酸化ニッケル粉末とを含み、
前記酸化ニッケル粉末の平均粒径が前記金属ニッケル粉末の平均粒径の０．０１６６倍以上０．０８５倍以下であり、
前記金属ニッケル粉末および前記酸化ニッケル粉末の総酸素量が１.３質量％以上１．９質量％以下である、導電ペースト用粉末が提供される。
In order to solve the above problems, according to one aspect of the present invention,
Metallic nickel powder,
Including nickel oxide powder mixed with the metal nickel powder,
The average particle diameter of the nickel oxide powder is 0.0166 times or more and 0.085 times or less of the average particle diameter of the metal nickel powder,
A conductive paste powder is provided in which the total oxygen content of the metal nickel powder and the nickel oxide powder is 1.3% by mass or more and 1.9% by mass or less.
本発明の一態様によれば、熱処理後の導電性、および熱収縮特性を改善できる、導電ペースト用粉末が提供される。 According to one embodiment of the present invention, there is provided a conductive paste powder capable of improving the conductivity after heat treatment and the heat shrinkage characteristics.
以下、本発明を実施するための形態について説明する。 Hereinafter, modes for carrying out the present invention will be described.
（導電ペースト）
導電ペーストは、金属ニッケル粉末と、エチルセルロース等のバインダーと、ターピネオール等の有機溶剤とを含む。導電ペーストは、分散剤をさらに含んでもよい。導電ペーストは、バインダーや有機溶剤、分散剤を分解、揮発させる脱バインダー処理の後、還元雰囲気下で熱処理され、内部電極層や外部電極層、電気回路層などの導電層を形成する。導電ペーストは、多層セラミック回路基板や積層セラミックコンデンサなどの製造に用いられる。
(Conductive paste)
The conductive paste includes metallic nickel powder, a binder such as ethyl cellulose, and an organic solvent such as terpineol. The conductive paste may further contain a dispersant. The conductive paste is heat-treated in a reducing atmosphere after debinding to decompose and volatilize the binder, organic solvent, and dispersant, and forms conductive layers such as internal electrode layers, external electrode layers, and electric circuit layers. The conductive paste is used for manufacturing a multilayer ceramic circuit board, a multilayer ceramic capacitor, and the like.
例えば、積層セラミックコンデンサは、誘電体グリーンシート上に導電ペーストをスクリーン印刷したものを複数枚重ねて熱圧着し、脱バインダー処理の後、還元雰囲気下で熱処理して製造される。積層セラミックコンデンサは、誘電体グリーンシートを焼成してなる誘電体層と、導電ペーストの塗布層を焼成してなる内部電極層とを交互に重ねた構造を有する。 For example, a multilayer ceramic capacitor is manufactured by stacking a plurality of screen-printed conductive pastes on a dielectric green sheet, thermocompression bonding, debinding, and then heat-treating in a reducing atmosphere. The multilayer ceramic capacitor has a structure in which dielectric layers formed by firing a dielectric green sheet and internal electrode layers formed by firing a coating layer of a conductive paste are alternately stacked.
導電ペーストは、誘電体グリーンシート上に塗布され誘電体グリーンシートと共に焼成される場合、チタン酸バリウム粉末等の誘電体粉末をさらに含んでもよい。これにより、導電ペーストの塗布層と誘電体グリーンシートとの熱収縮差を小さくでき、クラックの発生を抑制できる。また、焼成後の誘電体層と導電層との密着性を高めることができる。 When the conductive paste is applied onto the dielectric green sheet and fired together with the dielectric green sheet, the conductive paste may further include a dielectric powder such as barium titanate powder. Thereby, the thermal contraction difference between the coating layer of the conductive paste and the dielectric green sheet can be reduced, and the occurrence of cracks can be suppressed. In addition, the adhesion between the fired dielectric layer and the conductive layer can be improved.
本実施形態の導電ペーストは、金属ニッケル粉末が熱処理によって連続的につながるときに生じる熱収縮を低減するため、金属ニッケル粉末の他に、金属ニッケル粉末と混在する酸化ニッケル粉末をさらに含む。酸化ニッケル粉末は、金属ニッケル粉末の隙間を埋め、金属ニッケル粉末の熱収縮を低減する。 The conductive paste of the present embodiment further includes nickel oxide powder mixed with the metal nickel powder in addition to the metal nickel powder in order to reduce thermal shrinkage that occurs when the metal nickel powder is continuously connected by heat treatment. The nickel oxide powder fills the gap between the metallic nickel powders and reduces the thermal shrinkage of the metallic nickel powder.
金属ニッケル粉末の隙間を埋める材料として、金属粉末ではなく酸化物粉末を用いる理由は、酸化物粉末は微粉であっても凝集しにくく、金属ニッケル粉末の隙間に入り込みやすいからである。また、酸化物粉末として、酸化ニッケル粉末を用いる理由は、還元雰囲気下での熱処理によって酸化ニッケルの少なくとも一部が金属ニッケルに還元され、導電層の導電率が高くなるからである。 The reason why the oxide powder is used instead of the metal powder as a material for filling the gap between the metal nickel powders is that the oxide powder is not easily agglomerated even if it is a fine powder, and easily enters the gaps between the metal nickel powders. The reason why nickel oxide powder is used as the oxide powder is that at least part of nickel oxide is reduced to metallic nickel by heat treatment in a reducing atmosphere, and the conductivity of the conductive layer is increased.
金属ニッケル粉末と酸化ニッケル粉末とは、別々に製造され、混合して用いられてよい。金属ニッケル粉末と酸化ニッケル粉末とで導電ペースト用粉末が構成される。導電ペースト用粉末は、以下の説明では、金属ニッケル粉末と酸化ニッケル粉末のみを含み、誘電体粉末などを含まないが、誘電体粉末などを含んでもよい。以下、導電ペースト用粉末について説明する。 The metallic nickel powder and the nickel oxide powder may be manufactured separately and used in combination. The metal paste powder and the nickel oxide powder constitute a conductive paste powder. In the following description, the conductive paste powder includes only metallic nickel powder and nickel oxide powder and does not include dielectric powder, but may include dielectric powder. Hereinafter, the powder for conductive paste will be described.
（金属ニッケル粉末）
金属ニッケル粉末は、平均粒径が０．３μｍ以上であることが望ましい。金属ニッケル粉末の平均粒径は、詳しくは後述するが、ＳＥＭ像上での各粒子の面積円相当径を平均化して求める。金属ニッケル粉末の平均粒径が０．３μｍ以上であると、焼成時にクラックの発生を抑制できる。導電層の薄型化の観点から、金属ニッケル粉末の平均粒径は０．６μｍ以下であることが望ましい。金属ニッケル粉末の平均粒径が０．６μｍ以下であると、積層セラミックコンデンサの内部電極層を薄型化でき、積層セラミックコンデンサの小型化や高容量化を達成できる。
(Metallic nickel powder)
The metallic nickel powder desirably has an average particle size of 0.3 μm or more. Although the average particle diameter of the nickel metal powder will be described in detail later, it is obtained by averaging the area equivalent circle diameter of each particle on the SEM image. Generation | occurrence | production of a crack can be suppressed at the time of baking as the average particle diameter of metallic nickel powder is 0.3 micrometer or more. From the viewpoint of reducing the thickness of the conductive layer, the average particle size of the metallic nickel powder is desirably 0.6 μm or less. When the average particle diameter of the metallic nickel powder is 0.6 μm or less, the internal electrode layer of the multilayer ceramic capacitor can be thinned, and the multilayer ceramic capacitor can be reduced in size and increased in capacity.
金属ニッケル粉末は、充填性を高めるため、凝結粒子の少ないものが望ましく、さらに、粒度分布を有しているものが望ましい。金属ニッケル粉末の粒度分布は、好ましくは、Ｄ１０／Ｄ５０が０．２以上０．７以下であって、且つＤ９０／Ｄ５０が１．４以上５．０以下である。ここで、Ｄ１０とは、各粒径における粒子数を粒径の小さい側から累積し、その累積体積が全粒子の合計体積の１０％となる粒径を意味する。Ｄ５０とは、同様に粒子数を累積し、その累積体積が全粒子の合計体積の５０％となる粒径を意味する。Ｄ９０とは、同様に粒子数を累積し、その累積体積が全粒子の合計体積の９０％となる粒径を意味する。各粒子の粒径は、ＳＥＭ像上での面積円相当径として求める。 In order to improve the filling property, the metal nickel powder preferably has few condensed particles, and more preferably has a particle size distribution. The particle size distribution of the metallic nickel powder is preferably such that D10 / D50 is 0.2 or more and 0.7 or less, and D90 / D50 is 1.4 or more and 5.0 or less. Here, D10 means a particle size in which the number of particles in each particle size is accumulated from the smaller particle size side and the accumulated volume becomes 10% of the total volume of all particles. D50 means a particle size in which the number of particles is similarly accumulated and the accumulated volume is 50% of the total volume of all particles. Similarly, D90 means a particle size in which the number of particles is accumulated and the accumulated volume is 90% of the total volume of all particles. The particle diameter of each particle is determined as the area circle equivalent diameter on the SEM image.
金属ニッケル粉末は、大気中で放置すると、大気中に含まれる酸素などによって形成される酸化膜で覆われる。金属ニッケル粉末の酸素量は、後述の金属ニッケル粉末および酸化ニッケル粉末の総酸素量との関係から、好ましくは１．２質量％以下、より好ましくは１．０質量％以下である。また、金属ニッケル粉末の酸素量は、取扱い性の観点から、好ましくは０．５質量％以上である。 When the metallic nickel powder is left in the atmosphere, it is covered with an oxide film formed by oxygen contained in the atmosphere. The amount of oxygen in the metal nickel powder is preferably 1.2% by mass or less, more preferably 1.0% by mass or less, in relation to the total oxygen amount of the metal nickel powder and nickel oxide powder described later. The oxygen content of the metallic nickel powder is preferably 0.5% by mass or more from the viewpoint of handleability.
金属ニッケル粉末の製造方法としては、特に限定されないが、例えば、ニッケル塩ガスを還元ガスで還元する化学気相法、ニッケル塩水溶液を還元水溶液で還元する湿式還元法、固体のニッケル化合物を還元ガスで還元する固相法などが用いられる。これらの中でも、コストの観点から、固相法が特に好ましい。 The method for producing the metallic nickel powder is not particularly limited. For example, a chemical vapor phase method in which nickel salt gas is reduced with a reducing gas, a wet reduction method in which an aqueous nickel salt solution is reduced with a reducing aqueous solution, and a solid nickel compound is reduced into a reducing gas. For example, a solid phase method in which the reduction is performed is used. Among these, the solid phase method is particularly preferable from the viewpoint of cost.
湿式還元法では、ニッケル塩水溶液中でヒドラジン等の還元剤を用いて金属ニッケル粉末を晶析させる。ニッケル塩としては、特に限定されないが、例えば、塩化ニッケル、硝酸ニッケルおよび硫酸ニッケル等から選ばれる少なくとも１種類が用いられる。例えば６０ｇ／ｌの塩化ニッケル水溶液３００ｍｌを８０℃に保持した状態で攪拌しつつ６０％ヒドラジン水和物（ニッケル１モルに対して１．８モル）を添加し、次いで得られるスラリーに水酸化ナトリウム溶液を添加してｐＨ１２以上とする。これを攪拌しながら液温度を８０℃で１時間保持し、金属ニッケル粉末を晶析させ、ろ過乾燥させる。 In the wet reduction method, metallic nickel powder is crystallized using a reducing agent such as hydrazine in an aqueous nickel salt solution. Although it does not specifically limit as nickel salt, For example, at least 1 sort (s) chosen from nickel chloride, nickel nitrate, nickel sulfate, etc. is used. For example, 60% hydrazine hydrate (1.8 mol with respect to 1 mol of nickel) is added with stirring while maintaining 300 ml of a 60 g / l nickel chloride aqueous solution at 80 ° C., and then sodium hydroxide is added to the resulting slurry. Add the solution to pH 12 or higher. While stirring this, the liquid temperature is maintained at 80 ° C. for 1 hour to crystallize the metallic nickel powder, and then filter dry.
固相法では、例えば、塩化ニッケル溶液を水酸化ナトリウム溶液で中和して水酸化ニッケル粉末を析出し、析出した水酸化ニッケル粉末をろ過等で固液分離し、洗浄後に乾燥したうえで、還元ガスで還元することにより金属ニッケル粉末を得る。還元ガスは水素ガスと窒素ガスの混合ガス、混合ガスに占める水素ガスの割合は８０体積％以上９０体積％以下、還元温度は４５０℃以上６５０℃以下、還元時間は１．５時間以上４時間以下である。 In the solid phase method, for example, a nickel chloride solution is neutralized with a sodium hydroxide solution to precipitate a nickel hydroxide powder, and the precipitated nickel hydroxide powder is separated into solid and liquid by filtration or the like, dried after washing, Metal nickel powder is obtained by reducing with a reducing gas. The reducing gas is a mixed gas of hydrogen gas and nitrogen gas, the proportion of hydrogen gas in the mixed gas is 80 volume% to 90 volume%, the reduction temperature is 450 ° C. to 650 ° C., the reduction time is 1.5 hours to 4 hours It is as follows.
（酸化ニッケル粉末）
酸化ニッケル粉末は、金属ニッケル粉末と混在する。酸化ニッケル粉末は、金属ニッケル粉末の隙間に充填されるように、金属ニッケル粉末よりも小さい平均粒径を有する。酸化ニッケル粉末の平均粒径は、例えば金属ニッケル粉末の平均粒径の０．０１６６倍以上０．０８５倍以下である。酸化ニッケル粉末の平均粒径は、多検体比表面積測定装置を用いてＢＥＴ法で比表面積を測定し、その比表面積から換算し求める。
(Nickel oxide powder)
Nickel oxide powder is mixed with metallic nickel powder. The nickel oxide powder has an average particle size smaller than that of the metal nickel powder so as to fill a gap between the metal nickel powders. The average particle diameter of the nickel oxide powder is, for example, 0.0166 times or more and 0.085 times or less of the average particle diameter of the metallic nickel powder. The average particle diameter of the nickel oxide powder is determined by measuring the specific surface area by a BET method using a multi-specimen specific surface area measuring device and converting from the specific surface area.
酸化ニッケル粉末の平均粒径は、製造コストの観点から、好ましくは０．０１μｍ以上０．０５μｍ以下である。平均粒径が０．０１μｍ以上０．０５μｍ以下である酸化ニッケル粉末は、水酸化ニッケルや硫酸ニッケルなどの固体のニッケル化合物の粉末を焙焼することで容易に得られる。 The average particle diameter of the nickel oxide powder is preferably 0.01 μm or more and 0.05 μm or less from the viewpoint of manufacturing cost. A nickel oxide powder having an average particle size of 0.01 μm or more and 0.05 μm or less can be easily obtained by baking a powder of a solid nickel compound such as nickel hydroxide or nickel sulfate.
酸化ニッケル粉末は、金属ニッケル粉末の隙間に充填されやすいように、流動性を高めるため、凝結粒子の少ないものが望ましい。 The nickel oxide powder preferably has a small amount of condensed particles in order to enhance fluidity so that the gap between the metal nickel powders can be easily filled.
また、酸化ニッケル粉末は、金属ニッケル粉末の隙間に充填されやすいように、流動性を高めるため、金属ニッケル粉末に固着していないことが望ましい。従って、酸化ニッケル粉末は、金属ニッケル粉末とは別に製造され、混合されることが望ましい。 Further, it is desirable that the nickel oxide powder is not fixed to the metal nickel powder in order to enhance fluidity so that the gap between the metal nickel powders can be easily filled. Therefore, it is desirable that the nickel oxide powder is manufactured and mixed separately from the nickel metal powder.
尚、本実施形態の酸化ニッケル粉末は、金属ニッケル粉末とは別に製造され、混合されるが、本発明はこれに限定されない。つまり、酸化ニッケル粉末は、金属ニッケル粉末と同時に製造されてもよい。例えば金属ニッケル粉末の製造方法として固相法が用いられる場合、還元時間が１．５時間未満であると、金属ニッケル粉末中に酸化ニッケル粉末を残留させることができる。 In addition, although the nickel oxide powder of this embodiment is manufactured and mixed separately from metallic nickel powder, this invention is not limited to this. That is, the nickel oxide powder may be manufactured simultaneously with the metallic nickel powder. For example, when a solid phase method is used as a method for producing metallic nickel powder, the nickel oxide powder can remain in the metallic nickel powder when the reduction time is less than 1.5 hours.
酸化ニッケル粉末の残留量が多い場合、洗浄工程で酸化ニッケル粉末の量を調整することもできる。酸化ニッケル粉末は、金属ニッケル粉末よりも小さいので、洗浄液中で金属ニッケル粉末よりも沈降しにくい。沈降速度の差を利用して、洗浄工程で酸化ニッケル粉末の量を調整可能である。 When there is much residual amount of nickel oxide powder, the quantity of nickel oxide powder can also be adjusted at a washing | cleaning process. Since the nickel oxide powder is smaller than the metal nickel powder, it is less likely to settle in the cleaning liquid than the metal nickel powder. The amount of nickel oxide powder can be adjusted in the washing step by using the difference in settling speed.
（金属ニッケル粉末と酸化ニッケル粉末の総特性）
金属ニッケル粉末と酸化ニッケル粉末の総酸素量が大きいほど、金属ニッケル粉末に対する酸化ニッケル粉末の割合が多くなる。金属ニッケル粉末に対する酸化ニッケル粉末の割合が多過ぎても少な過ぎても、導電ペーストの塗布層における金属ニッケル粉末と酸化ニッケル粉末の充填性が悪くなり、導電層の導電性が悪くなる。
(Total characteristics of nickel metal powder and nickel oxide powder)
The ratio of the nickel oxide powder to the metal nickel powder increases as the total oxygen amount of the metal nickel powder and the nickel oxide powder increases. When the ratio of the nickel oxide powder to the metal nickel powder is too large or too small, the filling property of the metal nickel powder and the nickel oxide powder in the coating layer of the conductive paste is deteriorated, and the conductivity of the conductive layer is deteriorated.
金属ニッケル粉末に対する酸化ニッケル粉末の割合は、酸化ニッケル粉末が金属ニッケル粉末の隙間を埋める程度であることが望ましい。そのため、金属ニッケル粉末と酸化ニッケル粉末の総酸素量は、１．３質量％以上１．９質量％以下であることが望ましい。 The ratio of the nickel oxide powder to the metal nickel powder is desirably such that the nickel oxide powder fills the gap between the metal nickel powder. For this reason, the total oxygen content of the metal nickel powder and the nickel oxide powder is desirably 1.3% by mass or more and 1.9% by mass or less.
金属ニッケル粉末と酸化ニッケル粉末の総比表面積が小さいほど、金属ニッケル粉末と酸化ニッケル粉末の平均粒径が大きくなり、導電層の空隙率が少なくなる反面、導電層の厚さが厚くなる。そこで、導電層の空隙率の低下と導電層の薄型化とを両立するため、金属ニッケル粉末と酸化ニッケル粉末の総比表面積は２．５ｍ２／ｇ以上４．６ｍ２／ｇ以下であることが望ましい。 The smaller the total specific surface area of the metallic nickel powder and the nickel oxide powder is, the larger the average particle diameter of the metallic nickel powder and the nickel oxide powder is, and the lower the porosity of the conductive layer is, but the thicker the conductive layer is. Therefore, in order to achieve both reduction of the porosity of the conductive layer and thinning of the conductive layer, the total specific surface area of the metallic nickel powder and the nickel oxide powder is 2.5 m 2 / g or more and 4.6 m 2 / g or less. Is desirable.
金属ニッケル粉末と酸化ニッケル粉末の熱収縮挙動は、金属ニッケル粉末と酸化ニッケル粉末を金型に充填し、２００ｋｇｆ／ｃｍ２で加圧成形したペレットを用いて調べる。ペレットは、直径が５ｍｍの円柱状に成形される。ペレットには、バインダーや有機溶剤などは含まれない。尚、上述の如く、室温（例えば２５℃）下の導電ペーストには、バインダーや有機溶剤などが含まれる。しかし、導電ペーストを焼成して電極層を形成する場合、特に、本発明では重要とする９００℃から１３００℃の間の温度域では、該導電ペースト中のバインダーや有機溶剤は、分解等により除去されているので、本発明に係る金属ニッケル粉末と酸化ニッケル粉末のペレットの熱収縮挙動が、本発明に係る金属ニッケル粉末と酸化ニッケル粉末を用いた導電ペーストの９００℃から１３００の間の温度域の熱収縮挙動を表せるのである。 The thermal shrinkage behavior of the metallic nickel powder and the nickel oxide powder is examined using pellets that are filled with a metallic nickel powder and a nickel oxide powder and press-molded at 200 kgf / cm 2 . The pellet is formed into a cylindrical shape having a diameter of 5 mm. The pellet does not contain binders or organic solvents. As described above, the conductive paste at room temperature (for example, 25 ° C.) includes a binder, an organic solvent, and the like. However, when the electrode layer is formed by baking the conductive paste, particularly in the temperature range between 900 ° C. and 1300 ° C., which is important in the present invention, the binder and the organic solvent in the conductive paste are removed by decomposition or the like. Therefore, the thermal shrinkage behavior of the metal nickel powder and nickel oxide powder pellets according to the present invention is in the temperature range between 900 ° C. and 1300 of the conductive paste using the metal nickel powder and nickel oxide powder according to the present invention. The heat shrinkage behavior can be expressed.
ペレットの熱収縮挙動は、還元雰囲気下で、ペレットを室温から１３００℃まで５℃／ｍｉｎの昇温速度で加熱して調べる。還元雰囲気は水素と窒素の混合ガスで形成され、水素の含有量は２体積％である。 The thermal shrinkage behavior of the pellet is examined by heating the pellet from room temperature to 1300 ° C. at a rate of 5 ° C./min in a reducing atmosphere. The reducing atmosphere is formed of a mixed gas of hydrogen and nitrogen, and the hydrogen content is 2% by volume.
還元雰囲気下でペレットを焼成すると、金属ニッケル粉末同士が連続的につながるため、また、酸化ニッケル粉末の少なくとも一部が還元されるため、ペレットが収縮する。 When the pellets are fired in a reducing atmosphere, the metal nickel powders are continuously connected to each other, and at least a part of the nickel oxide powders are reduced, so that the pellets shrink.
９００℃から１３００℃までの間のペレットの熱収縮挙動が重要である。９００℃未満の温度では、ペレットには含まれないが導電ペーストには含まれる、バインダーや有機溶剤などの分解、揮発による収縮が支配的になるためである。バインダーなどは導電ペーストの塗布層および誘電体シートの両方に含まれるため、９００℃未満の温度では、導電ペーストの塗布層の熱収縮挙動と、誘電体シートの熱収縮挙動とが一致する。 The heat shrink behavior of the pellets between 900 ° C. and 1300 ° C. is important. This is because at temperatures below 900 ° C., shrinkage due to decomposition and volatilization of the binder and organic solvent, which are not included in the pellets but are included in the conductive paste, becomes dominant. Since the binder and the like are included in both the conductive paste coating layer and the dielectric sheet, the thermal shrinkage behavior of the conductive paste coating layer and the thermal shrinkage behavior of the dielectric sheet match at temperatures below 900 ° C.
各温度でのペレットの体積（Ｖ）は、室温（例えば２５℃）でのペレットの体積（Ｖ０）に対する比率［単位：％］で表す。室温でのペレットの体積（Ｖ０）が１００％である。Ｖ０からＶを引いた値（Ｖ０−Ｖ）は、収縮率を表す。 The pellet volume (V) at each temperature is expressed as a ratio [unit:%] to the pellet volume (V0) at room temperature (for example, 25 ° C.). The volume of the pellet at room temperature (V0) is 100%. A value obtained by subtracting V from V0 (V0-V) represents a contraction rate.
９００℃でのペレットの体積（Ｖ１）と１３００℃でのペレットの体積（Ｖ２）との差（Ｖ２−Ｖ１）が−０．４％以上０％以下であることが望ましい。差（Ｖ２−Ｖ１）が−０．４％以上０％以下であると、９００℃以上での、導電ペーストの塗布層の熱収縮挙動と、誘電体シートの熱収縮挙動とが一致するため、歪の発生を抑制でき、クラックの発生を抑制できる。 The difference (V2−V1) between the pellet volume (V1) at 900 ° C. and the pellet volume (V2) at 1300 ° C. is preferably −0.4% or more and 0% or less. When the difference (V2−V1) is −0.4% or more and 0% or less, the heat shrinkage behavior of the coating layer of the conductive paste and the heat shrinkage behavior of the dielectric sheet at 900 ° C. or more match. Generation | occurrence | production of distortion can be suppressed and generation | occurrence | production of a crack can be suppressed.
（導電層の製造方法）
導電層の製造方法は、上記導電ペースト用粉末を含む導電ペーストの塗布層を焼成して、導電層を形成する焼成工程を有する。本実施形態の導電ペーストは、金属ニッケル粉末の他に、酸化ニッケル粉末をさらに含む。酸化ニッケル粉末は、金属ニッケル粉末の隙間を埋め、金属ニッケル粉末の熱収縮を低減する。
(Method for producing conductive layer)
The manufacturing method of a conductive layer has a baking process of baking the application layer of the conductive paste containing the said powder for conductive pastes, and forming a conductive layer. The conductive paste of the present embodiment further includes nickel oxide powder in addition to the metallic nickel powder. The nickel oxide powder fills the gap between the metallic nickel powders and reduces the thermal shrinkage of the metallic nickel powder.
焼成工程は、還元雰囲気下で上記導電ペーストを焼成して、導電ペーストに含まれる酸化ニッケルの少なくとも一部を金属ニッケルに還元する還元工程を含む。還元雰囲気下での熱処理によって酸化ニッケルの少なくとも一部が金属ニッケルに還元され、導電層の導電率を向上できる。 The firing step includes a reduction step of firing the conductive paste in a reducing atmosphere to reduce at least part of the nickel oxide contained in the conductive paste to metallic nickel. By heat treatment in a reducing atmosphere, at least a part of nickel oxide is reduced to metallic nickel, and the conductivity of the conductive layer can be improved.
還元工程での還元雰囲気は例えば水素と窒素の混合ガスで形成され、水素の含有量は特に限定されないが例えば２体積％である。還元工程での焼成温度は、特に限定されないが、例えば９００℃以上１３００℃以下である。 The reducing atmosphere in the reduction step is formed of, for example, a mixed gas of hydrogen and nitrogen, and the hydrogen content is not particularly limited, but is, for example, 2% by volume. Although the calcination temperature in a reduction process is not specifically limited, For example, they are 900 degreeC or more and 1300 degrees C or less.
上記製造方法で得られる導電層は、例えば積層セラミックコンデンサの内部電極層として用いられる。尚、導電層は、外部電極層や電気回路層として用いられてもよい。 The conductive layer obtained by the above manufacturing method is used, for example, as an internal electrode layer of a multilayer ceramic capacitor. The conductive layer may be used as an external electrode layer or an electric circuit layer.
以下、具体的な実施例や比較例などについて説明する。以下で説明する例１〜例７のうち、例１〜例４が実施例、例５〜例７が比較例である。例１〜例７では、金属ニッケル粉末と酸化ニッケル粉末とを混合した導電ペースト用粉末、または金属ニッケル粉末を加圧成形して円柱状のペレットを作成し、そのペレットの熱収縮挙動などを調べた。例１〜例６において、導電ペースト用粉末は、金属ニッケル粉末と酸化ニッケル粉末のみを含み、誘電体粉末などを含まない。 Hereinafter, specific examples and comparative examples will be described. Of Examples 1 to 7 described below, Examples 1 to 4 are Examples, and Examples 5 to 7 are Comparative Examples. In Examples 1 to 7, a powder for a conductive paste in which metallic nickel powder and nickel oxide powder are mixed, or pressure-molding metallic nickel powder to form a cylindrical pellet, and the heat shrinkage behavior of the pellet is examined. It was. In Examples 1 to 6, the conductive paste powder includes only metallic nickel powder and nickel oxide powder, and does not include dielectric powder.
［評価方法］
先ず、評価方法について説明する。
[Evaluation method]
First, the evaluation method will be described.
（１）導電ペースト用粉末の総酸素量、および金属ニッケル粉末の酸素量は、酸素・窒素・アルゴン分析装置（ＬＥＣＯ社製、ＴＣ-４３６ＡＲ）を用いて、不活性ガスインパルス加熱融解赤外吸収法により測定した。 (1) The total amount of oxygen in the conductive paste powder and the amount of oxygen in the metallic nickel powder were measured using an oxygen / nitrogen / argon analyzer (LECO, TC-436AR) and inert gas impulse heating and melting infrared absorption. Measured by the method.
（２）導電ペースト用粉末の総比表面積、および金属ニッケル粉末の比表面積は、多検体比表面積測定装置（ユアサアイオミクス株式会社製、マルチソーブ）を用いて、ＢＥＴ法で求めた。 (2) The total specific surface area of the conductive paste powder and the specific surface area of the metallic nickel powder were determined by the BET method using a multi-specimen specific surface area measuring device (manufactured by Yuasa Iomics Co., Ltd., Multisorb).
（３）金属ニッケル粉末の平均粒径は、走査型電子顕微鏡（ＳＥＭ：Scanning Electron Microscope、日本電子社製、ＪＳＭ−５５１０）を用いて撮像したＳＥＭ像上での各粒子の面積円相当径を平均化して求めた。ＳＥＭ像の倍率は２０００倍、ＳＥＭ像の撮像範囲は縦１９．２μｍ、横２５．６μｍであった。 (3) The average particle diameter of the metallic nickel powder is the area equivalent circle diameter of each particle on the SEM image picked up using a scanning electron microscope (SEM: Scanning Electron Microscope, JEOL Ltd., JSM-5510). Obtained by averaging. The magnification of the SEM image was 2000 times, and the imaging range of the SEM image was 19.2 μm in length and 25.6 μm in width.
（４）酸化ニッケル粉末の平均粒径は、多検体比表面積測定装置（ユアサアイオミクス株式会社マルチソーブ）を用いてＢＥＴ法で比表面積を測定し、その比表面積から換算して求めた。 (4) The average particle diameter of the nickel oxide powder was determined by measuring the specific surface area by the BET method using a multi-specimen specific surface area measuring device (Yuasa Iomics Co., Ltd. Multisorb) and converting from the specific surface area.
（５）ペレットの熱収縮挙動は、熱機械的分析装置（ＴＭＡ：Thermo Mechanical Analyzer、マックサイエンス社製、ＴＭＡ４０００Ｓ）を用いて測定した。この測定では、ペレットを還元雰囲気中で室温から１３００℃まで５℃／ｍｉｎの昇温速度で加熱した。還元雰囲気は水素と窒素の混合ガスで形成し、水素の含有量は２体積％であった。測定したペレットの収縮曲線から、９００℃でのペレットの体積（Ｖ１）と１３００℃でのペレットの体積（Ｖ２）との差（Ｖ２−Ｖ１）を求めた。 (5) The thermal contraction behavior of the pellet was measured using a thermomechanical analyzer (TMA: Thermo Mechanical Analyzer, manufactured by Mac Science, TMA4000S). In this measurement, the pellet was heated in a reducing atmosphere from room temperature to 1300 ° C. at a rate of 5 ° C./min. The reducing atmosphere was formed of a mixed gas of hydrogen and nitrogen, and the hydrogen content was 2% by volume. From the measured shrinkage curve of the pellet, the difference (V2−V1) between the pellet volume (V1) at 900 ° C. and the pellet volume (V2) at 1300 ° C. was determined.
［例１］
例１のペレット材料としては、金属ニッケル粉末と酸化ニッケル粉末とを混合した導電ペースト用粉末を用いた。金属ニッケル粉末と酸化ニッケル粉末とは、別々に製造したうえで、混合した。
[Example 1]
As the pellet material of Example 1, a conductive paste powder in which metallic nickel powder and nickel oxide powder were mixed was used. The metallic nickel powder and the nickel oxide powder were mixed and manufactured separately.
金属ニッケル粉末は、空気中で水酸化ニッケル粉末を４８０℃で２時間焙焼して得た酸化ニッケルを、還元雰囲気中で４８０℃で２時間焼成して得た。還元雰囲気は水素ガスと窒素ガスの混合ガスで構成し、混合ガスに占める水素ガスの割合は８０体積％とした。金属ニッケル粉末は、平均粒径が０.５μｍ、酸素量が１．１質量％であった。 The nickel metal powder was obtained by calcining nickel oxide powder in air at 480 ° C. for 2 hours and firing it in a reducing atmosphere at 480 ° C. for 2 hours. The reducing atmosphere was composed of a mixed gas of hydrogen gas and nitrogen gas, and the proportion of hydrogen gas in the mixed gas was 80% by volume. The metal nickel powder had an average particle size of 0.5 μm and an oxygen content of 1.1% by mass.
一方、酸化ニッケル粉末は、空気中で水酸化ニッケル粉末を４８０℃で２時間焙焼して得た。酸化ニッケル粉末の平均粒径は０．０１μｍであった。 On the other hand, nickel oxide powder was obtained by roasting nickel hydroxide powder in air at 480 ° C. for 2 hours. The average particle diameter of the nickel oxide powder was 0.01 μm.
例１で作製した導電ペースト用粉末は、総酸素量が１．８質量％、総比表面積が２．９ｍ２／ｇであった。 The conductive paste powder produced in Example 1 had a total oxygen content of 1.8% by mass and a total specific surface area of 2.9 m 2 / g.
［例２］
例２のペレット材料としては、例１と同一条件で作製した金属ニッケル粉末と、例１と同一条件で作製した酸化ニッケル粉末とを、例１とは異なる割合で混合した導電ペースト用粉末を用いた。
[Example 2]
As the pellet material of Example 2, a conductive paste powder in which metallic nickel powder produced under the same conditions as in Example 1 and nickel oxide powder produced under the same conditions as in Example 1 were mixed at a different ratio from Example 1 was used. It was.
例２で作製した導電ペースト用粉末は、総酸素量が１．３質量％、総比表面積が２．５ｍ２／ｇであった。 The conductive paste powder produced in Example 2 had a total oxygen content of 1.3% by mass and a total specific surface area of 2.5 m 2 / g.
［例３］
例３のペレット材料としては、例１とは水酸化ニッケル粉末の平均粒径が異なる以外、例１と同一条件で作製した金属ニッケル粉末と、例１と同一条件で作製した酸化ニッケル粉末とを混合した導電ペースト用粉末を用いた。
[Example 3]
As the pellet material of Example 3, a nickel metal powder produced under the same conditions as in Example 1 and a nickel oxide powder produced under the same conditions as in Example 1 except that the average particle diameter of the nickel hydroxide powder is different from that in Example 1. The mixed conductive paste powder was used.
例３で作製した金属ニッケル粉末は、平均粒径が０．３μｍ、酸素量が１．５質量％であった。 The metallic nickel powder produced in Example 3 had an average particle size of 0.3 μm and an oxygen content of 1.5% by mass.
また、例３で作製した導電ペースト用粉末は、総酸素量が１．９質量％、総比表面積が４．６ｍ２／ｇであった。 The conductive paste powder produced in Example 3 had a total oxygen content of 1.9% by mass and a total specific surface area of 4.6 m 2 / g.
［例４］
例４のペレット材料としては、例３と同一条件で作製した金属ニッケル粉末と、例３と同一条件で作製した酸化ニッケル粉末とを、例３とは異なる割合で混合した導電ペースト用粉末を用いた。
[Example 4]
As the pellet material of Example 4, a conductive paste powder in which metallic nickel powder produced under the same conditions as in Example 3 and nickel oxide powder produced under the same conditions as in Example 3 were mixed at a different ratio from Example 3 was used. It was.
例４で作製した導電ペースト用粉末は、総酸素量が１．４質量％、総比表面積が３．７ｍ２／ｇであった。 The conductive paste powder produced in Example 4 had a total oxygen content of 1.4% by mass and a total specific surface area of 3.7 m 2 / g.
［例５］
例５のペレット材料としては、例１と同一条件で作製した金属ニッケル粉末と、例１と同一条件で作製した酸化ニッケル粉末とを、例１とは異なる割合で混合した導電ペースト用粉末を用いた。
[Example 5]
As the pellet material of Example 5, a conductive paste powder in which metallic nickel powder produced under the same conditions as in Example 1 and nickel oxide powder produced under the same conditions as in Example 1 were mixed at a different ratio from Example 1 was used. It was.
例５で作製した導電ペースト用粉末は、総酸素量が２．０質量％、総比表面積が３．０ｍ２／ｇであった。 The conductive paste powder produced in Example 5 had a total oxygen content of 2.0 mass% and a total specific surface area of 3.0 m 2 / g.
［例６］
例６のペレット材料としては、例３と同一条件で作製した金属ニッケル粉末と、例３と同一条件で作製した酸化ニッケル粉末とを、例３とは異なる割合で混合した導電ペースト用粉末を用いた。
[Example 6]
As the pellet material of Example 6, a conductive paste powder prepared by mixing metallic nickel powder produced under the same conditions as in Example 3 and nickel oxide powder produced under the same conditions as in Example 3 at a different ratio from Example 3 was used. It was.
例６で作製した導電ペースト用粉末は、総酸素量が２．１質量％、総比表面積が４．８ｍ２／ｇであった。 The conductive paste powder produced in Example 6 had a total oxygen content of 2.1% by mass and a total specific surface area of 4.8 m 2 / g.
［例７］
例７のペレット材料としては、例３と同一条件で作製した金属ニッケル粉末を用いた。この金属ニッケル粉末は、酸化ニッケル粉末と混合せずに用いた。
[Example 7]
As the pellet material of Example 7, metallic nickel powder produced under the same conditions as in Example 3 was used. This metallic nickel powder was used without being mixed with the nickel oxide powder.
［評価結果］
図１に、例１、例２および例５のペレットの収縮曲線を示す。また、図２に、例３、例４、例６および例７のペレットの収縮曲線を示す。図１および図２において、横軸は温度、縦軸はＶ−Ｖ０である。さらに、表１に、金属ニッケル粉末の平均粒径Ｄ１、酸化ニッケル粉末の平均粒径Ｄ２、ペレット材料の総酸素量、ペレット材料の総比表面積、Ｄ２／Ｄ１、Ｖ２−Ｖ１を示す。
[Evaluation results]
In FIG. 1, the shrinkage | contraction curve of the pellet of Example 1, Example 2, and Example 5 is shown. FIG. 2 shows the shrinkage curves of the pellets of Example 3, Example 4, Example 6, and Example 7. 1 and 2, the horizontal axis represents temperature, and the vertical axis represents V-V0. Further, Table 1 shows the average particle diameter D1 of the nickel metal powder, the average particle diameter D2 of the nickel oxide powder, the total oxygen amount of the pellet material, the total specific surface area of the pellet material, D2 / D1, and V2-V1.
以上、導電ペースト用粉末の実施形態等について説明したが、本発明は上記実施形態等に限定されるものではなく、特許請求の範囲に記載された本発明の要旨の範囲内において、種々の変形、改良が可能である。 As mentioned above, although embodiment etc. of the powder for conductive paste were explained, the present invention is not limited to the above-mentioned embodiment etc., and in the range of the gist of the present invention indicated in the claim, various modifications are possible. Improvements are possible.
Claims (5)
前記金属ニッケル粉末と混在する酸化ニッケル粉末とを含み、
前記酸化ニッケル粉末の平均粒径が前記金属ニッケル粉末の平均粒径の０．０１６６倍以上０．０８５倍以下であり、
前記金属ニッケル粉末および前記酸化ニッケル粉末の総酸素量が１.３質量％以上１．９質量％以下である、導電ペースト用粉末。 Metallic nickel powder,
Including nickel oxide powder mixed with the metal nickel powder,
The average particle diameter of the nickel oxide powder is 0.0166 times or more and 0.085 times or less of the average particle diameter of the metal nickel powder,
The powder for electrically conductive paste whose total oxygen amount of the said metal nickel powder and the said nickel oxide powder is 1.3 to 1.9 mass%.
前記焼成工程は、還元雰囲気下で前記導電ペーストの前記塗布層を焼成して、前記導電ペーストに含まれる酸化ニッケルの少なくとも一部を金属ニッケルに還元する還元工程を含む、導電層の製造方法。 A firing step of firing a conductive paste coating layer containing the conductive paste powder according to any one of claims 1 to 3 to form a conductive layer,
The said baking process is a manufacturing method of a conductive layer including the reduction process which bakes the said coating layer of the said conductive paste in a reducing atmosphere, and reduces at least one part of the nickel oxide contained in the said conductive paste to metallic nickel.
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| JPH08246001A (en) * | 1995-03-10 | 1996-09-24 | Kawasaki Steel Corp | Nickel superfine powder for multilayer ceramic capacitor |
| JP2014136826A (en) * | 2013-01-18 | 2014-07-28 | Nippon Steel & Sumikin Chemical Co Ltd | Composite nickel particulate, and method of manufacturing the same |
| JP2015190043A (en) * | 2014-03-28 | 2015-11-02 | 住友金属鉱山株式会社 | Wet manufacturing process of nickel powder |
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| JPH0555077A (en) * | 1991-08-29 | 1993-03-05 | Dai Ichi Kogyo Seiyaku Co Ltd | Conductor paste for electrode of ceramic capacitor |
| JPH08246001A (en) * | 1995-03-10 | 1996-09-24 | Kawasaki Steel Corp | Nickel superfine powder for multilayer ceramic capacitor |
| JP2014136826A (en) * | 2013-01-18 | 2014-07-28 | Nippon Steel & Sumikin Chemical Co Ltd | Composite nickel particulate, and method of manufacturing the same |
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| WO2023002921A1 (en) * | 2021-07-21 | 2023-01-26 | 京セラ株式会社 | Conductive paste for forming electrode |
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