TW201842989A - Nickel powder and nickel paste - Google Patents

Nickel powder and nickel paste Download PDF

Info

Publication number
TW201842989A
TW201842989A TW107107994A TW107107994A TW201842989A TW 201842989 A TW201842989 A TW 201842989A TW 107107994 A TW107107994 A TW 107107994A TW 107107994 A TW107107994 A TW 107107994A TW 201842989 A TW201842989 A TW 201842989A
Authority
TW
Taiwan
Prior art keywords
nickel powder
nickel
less
gas
mass
Prior art date
Application number
TW107107994A
Other languages
Chinese (zh)
Other versions
TWI813559B (en
Inventor
本多雄大
淺井剛
吉田貢
Original Assignee
日商東邦鈦股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 日商東邦鈦股份有限公司 filed Critical 日商東邦鈦股份有限公司
Publication of TW201842989A publication Critical patent/TW201842989A/en
Application granted granted Critical
Publication of TWI813559B publication Critical patent/TWI813559B/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/12—Metallic powder containing non-metallic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form

Abstract

To provide a nickel powder and a nickel paste that is satisfactory as an internal electrode material for an MLCC and that has excellent debinding properties and improved dispersibility and wetting properties in a low-polarity solvent, particularly dihydroterpenyl acetate. A spherical nickel powder having a number-average diameter of 1 [mu]m or less and a crystallite diameter d of more than 40 nm, the nickel powder characterized in that the ratio (Ib/Ia) of the absorbance Ia at 1385 cm-1 and the absorbance Ib at 1600 cm-1 measured by Fourier-transform infrared spectroscopy is 0.8 or greater, and the carbon concentration is 0.05% by mass to 2.0% by mass. Here, the crystallite diameter d is calculated using the Scherrer equation (equation 2) by X-ray diffraction measurement for the (111) face, where K is the Scherrer constant, [lambda] is the measured X-ray wavelength, [beta] is the half-value width, and [Theta] is the diffraction angle.

Description

鎳粉及鎳糊  Nickel powder and nickel paste  

本發明關於適用於電子零件等中所使用之導電糊用途之鎳粉，特別是關於適合使用於積層陶瓷電容器的內部電極用途之導電糊的鎳粉。 The present invention relates to a nickel powder suitable for use in a conductive paste used in an electronic component or the like, and more particularly to a nickel powder suitable for use as a conductive paste for internal electrode use of a laminated ceramic capacitor.

積層陶瓷電容器(以下簡稱為「MLCC」)為介電體與導電體交互重疊而成的電子零件，被使用於如智慧型手機、平板終端機之電子設備中。 A multilayer ceramic capacitor (hereinafter referred to as "MLCC") is an electronic component in which a dielectric body and a conductor are alternately overlapped, and is used in an electronic device such as a smart phone or a tablet terminal.

一般來說，MLCC係如下製造。亦即，把將鈦酸鋇等的陶瓷粉末與有機黏結劑混合而成之介電體糊形成為薄片狀，來製作介電體胚片(green sheet)。另一方面，把內部電極用的金屬微粉末，及用於控制其燒結行為之陶瓷(以下稱為「共同材料(common material)」)，與有機溶劑、有機黏結劑等有機化合物混合，形成內部電極糊，將其印刷於介電體胚片上、乾燥。將經塗布此電極層之介電體胚片積層後，加熱加壓接著而形成積層體，加工成目標形狀。接著，為了去除有機黏結劑等的有機成分，在弱氧化氣體環境中對積層體施以加熱處理(以下將此稱為「去黏結劑處理」)，然後，在還原氣體環境中以1300℃左右的溫度燒製。最後，將外部電極燒接在積層體的外側上得到MLCC。 Generally, MLCC is manufactured as follows. In other words, a dielectric paste in which a ceramic powder such as barium titanate or the like is mixed with an organic binder is formed into a sheet shape to form a dielectric green sheet. On the other hand, the metal fine powder for the internal electrode and the ceramic for controlling the sintering behavior (hereinafter referred to as "common material") are mixed with an organic compound such as an organic solvent or an organic binder to form an internal portion. The electrode paste was printed on a dielectric blank and dried. After the dielectric green sheets coated with the electrode layers are laminated, they are heated and pressed to form a layered body, which is processed into a target shape. Next, in order to remove an organic component such as an organic binder, the laminate is subjected to heat treatment in a weak oxidizing gas atmosphere (hereinafter referred to as "debonding agent treatment"), and then, in a reducing gas atmosphere, at about 1300 ° C. The temperature is fired. Finally, the external electrode is burned on the outside of the laminate to obtain MLCC.

近年來，伴隨著電子設備的小型化‧高功能化，MLCC也朝小型化‧大容量化發展，而要求內部電極層的薄膜化。內部電極用的金屬微粉末，粒徑為數十nm~數百nm。而過去雖使用鈀等的貴金屬，但比較便宜的鎳等之卑金屬的使用也在增加。 In recent years, with the miniaturization and high functionality of electronic equipment, the MLCC has also been miniaturized and expanded in capacity, and the internal electrode layer is required to be thinned. A metal fine powder for internal electrodes having a particle diameter of several tens nm to several hundreds nm. In the past, although precious metals such as palladium were used, the use of relatively inexpensive nickel such as nickel was also increasing.

MLCC的內部電極用鎳粉，可藉由例如使氯化鎳氣體與氫氣接觸之氣相反應法，以優異的生產性來合成平均粒徑為1μm以下且結晶性高的球狀鎳微粉。 The nickel powder is used for the internal electrode of the MLCC, and a spherical nickel fine powder having an average particle diameter of 1 μm or less and high crystallinity can be synthesized with excellent productivity by, for example, a gas phase reaction method in which nickel chloride gas is brought into contact with hydrogen gas.

另一方面，為了將內部電極薄膜化，當將鎳粉小粒徑化時，由於鎳粉的比表面積增加，鎳粉在液相中及氣相中會變得容易凝集。鎳粉若在內部電極糊中凝集，會因短路、分層而使MLCC的容量降低而成為問題。其中，短路係指因粗大粒子或凝集的鎳粉，讓內部電極層失去平坦性，使內部電極層的凹凸部貫穿介電體層之結構缺陷。又，分層係因凝集的鎳粉使得與共同材料的混合變的不充分，讓內部電極層與介電體層的熱收縮行為變得不一致的結果，於燒製時內部電極層與介電體層剝離之結構缺陷。因此，為了製作結構缺陷少、小型‧大容量的MLCC，而要求在內部電極糊中的分散性佳之鎳粉。 On the other hand, in order to thin the internal electrode, when the nickel powder is reduced in particle diameter, the nickel powder tends to aggregate in the liquid phase and in the gas phase due to an increase in the specific surface area of the nickel powder. When the nickel powder is aggregated in the internal electrode paste, the capacity of the MLCC is lowered due to short-circuiting or delamination, which is a problem. Here, the short circuit refers to a structural defect in which the internal electrode layer loses flatness due to coarse particles or agglomerated nickel powder, and the uneven portion of the internal electrode layer penetrates the dielectric layer. Further, the layered system is insufficient in mixing with the common material due to the agglomerated nickel powder, and the heat shrinkage behavior of the internal electrode layer and the dielectric layer is inconsistent, and the internal electrode layer and the dielectric layer are formed during firing. Stripped structural defects. Therefore, in order to produce a MLCC having a small structural defect and a small size and a large capacity, it is required to have a nickel powder which is excellent in dispersibility in the internal electrode paste.

為了提升鎳粉在內部電極糊中的分散性，提升對低極性溶劑的潤濕性為重要的。低極性溶劑係指HLB為2.5以下的溶劑，可列舉例如：己烷、甲苯、萜品醇、二氫萜品醇(dihydroterpineol)、二氫萜品醇乙酸酯等。又，下式1稱為WASHBURN的算式，其係關於 粒子在溶劑中之分散速度之理論式。其中，v為分散速度、η為溶劑黏度、L為細孔長度、r為細孔半徑、γL為溶劑的表面張力、θ為接觸角、△P為分散壓力。如此式所示，分散速度係由潤濕性(第1項)與分散壓力(第2項)的和來決定。亦即，一方面顯示若對任一粒子與溶劑施加高分散壓力即能分散，另一方面顯示若潤濕性高，即使分散壓力變小也能分散。 In order to improve the dispersibility of the nickel powder in the internal electrode paste, it is important to improve the wettability to the low-polar solvent. The low-polarity solvent refers to a solvent having an HLB of 2.5 or less, and examples thereof include hexane, toluene, terpineol, dihydroterpineol, and dihydroterpineol acetate. Further, the following formula 1 is called a formula of WASHBURN, which is a theoretical formula regarding the dispersion speed of particles in a solvent. Wherein v is the dispersion speed, η is the solvent viscosity, L is the pore length, r is the pore radius, γ L is the surface tension of the solvent, θ is the contact angle, and ΔP is the dispersion pressure. As shown in this formula, the dispersion speed is determined by the sum of wettability (item 1) and dispersion pressure (item 2). That is, on the other hand, it is shown that if any of the particles and the solvent are applied with a high dispersion pressure, they can be dispersed, and on the other hand, if the wettability is high, the dispersion can be dispersed even if the dispersion pressure is small.

關於一次粒子的平均粒徑為1μm以下，且在糊中的分散性優異之鎳奈米粒子之合成，例如提案有一種鎳奈米粒子之製造方法，其具有：調製羧酸鎳及1級胺的混合物之第一步驟；將前述混合物加熱並得到生成鎳錯合物之錯化反應液之第二步驟；及對前述錯化反應液照射微波，以200℃以上的溫度加熱，得到鎳奈米粒子漿料之第三步驟，於前述第三步驟中，係在前述錯化反應液中，存在有價數為3以上的多元羧酸之狀態下進行加熱(例如參照日本國專利公開公報第2011-214143號)。 In the synthesis of nickel nanoparticles having an average particle diameter of primary particles of 1 μm or less and excellent dispersibility in a paste, for example, a method for producing nickel nanoparticles is proposed, which comprises: preparing nickel carboxylate and a primary amine a first step of the mixture; heating the mixture to obtain a second step of generating a mis-formed reaction solution of the nickel complex; and irradiating the mis-action reaction liquid with microwaves and heating at a temperature of 200 ° C or higher to obtain nickel nanoparticles In the third step of the particle slurry, in the third step, heating is carried out in a state in which a polyvalent carboxylic acid having a valence of 3 or more is present (for example, refer to Japanese Patent Laid-Open No. 2011- No. 214143).

然而，日本特開2011-214143號公報中所列舉之以多元羧酸處理之鎳粉，雖然改善了在低極性溶劑中的分散性，但關於對低極性溶劑的潤濕性則完全沒有提及。因此，在施加弱的分散處理之情形下，則不清楚是否有優異的分散性。 However, the nickel powder treated with a polycarboxylic acid as exemplified in Japanese Laid-Open Patent Publication No. 2011-214143, although improving the dispersibility in a low polar solvent, has no mention at all regarding the wettability to a low polar solvent. . Therefore, in the case where a weak dispersion treatment is applied, it is not clear whether or not there is excellent dispersibility.

此外，日本特開2011-214143號公報中所列舉之以多元羧酸處理之鎳粉的碳含有率高。作為MLCC的內部電極使用之金屬粉，必須在去黏結劑步驟除去有機物，但就高碳含有率且含有分解溫度高的有機物的金屬粉而言，無法以去黏結劑處理完全去除有機物，而在接下去的燒製步驟中，殘留有機物會變成氣體，結果恐怕會成為結構缺陷的原因。 Further, the nickel powder treated with the polyvalent carboxylic acid as exemplified in Japanese Laid-Open Patent Publication No. 2011-214143 has a high carbon content. As the metal powder used as the internal electrode of the MLCC, it is necessary to remove the organic matter in the debonding step, but in the case of the metal powder having a high carbon content and containing an organic substance having a high decomposition temperature, it is impossible to completely remove the organic substance by the debonding agent treatment, and In the subsequent firing step, the residual organic matter becomes a gas, and as a result, it may become a cause of structural defects.

發明概要Summary of invention

本發明有鑑於上述先前技術的問題點，其目的為提供適合作為MLCC的內部電極材料，去黏結劑性優異、對低極性溶劑，特別是對二氫萜品醇乙酸酯的潤濕性及分散性經改善過之鎳粉及鎳糊。 The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide an internal electrode material suitable as an MLCC, which is excellent in debonding property, wettability to a low polar solvent, particularly to dihydroterpene alcohol acetate, and Nickel powder and nickel paste with improved dispersibility.

本發明之鎳粉係數量平均粒徑為1μm以下、微晶直徑d大於40nm的球狀鎳粉，其特徵為，以傅立葉轉換紅外光光度計(Fourier transform infrared spectrophotometer)測定時於1385cm-1之吸光度Ia與於1600cm-1之吸光度Ib的比(Ib/Ia)為0.8以上，碳濃度為0.05質量%以上2.0質量%以下。 The spherical nickel powder having a nickel powder coefficient average particle diameter of 1 μm or less and a crystallite diameter d of more than 40 nm is characterized in that it is measured at a temperature of 1385 cm -1 by a Fourier transform infrared spectrophotometer. The ratio (I b /I a ) of the absorbance I a to the absorbance I b at 1600 cm -1 is 0.8 or more, and the carbon concentration is 0.05% by mass or more and 2.0% by mass or less.

本發明中，較佳的態樣為於非活性環境下以300℃進行熱處理時之碳濃度的減少率為50%以上，與二氫萜品醇乙酸酯混合時，以鎳粉的每表面積之二氫萜品醇乙酸酯的添加量為0.02g‧m-2以下成為糊狀。 In the present invention, a preferred aspect is a carbon concentration reduction rate of 50% or more when heat-treated at 300 ° C in an inert environment, and a surface area of nickel powder when mixed with dihydroterpene alcohol acetate. The amount of the dihydroterpene alcohol acetate added is 0.02 g·m -2 or less to form a paste.

依據本發明之鎳粉，由於可改善對低極性溶劑，特別是對二氫萜品醇乙酸酯的潤濕性及分散性，故在使用作為MLCC用導電糊時，可抑制凝集粒子的產生，在MLCC的製造步驟中的去黏結劑性亦優異。藉此，能有助於製造短路與分層少的MLCC。 According to the nickel powder of the present invention, since the wettability and dispersibility of the low-polarity solvent, particularly the dihydroterpene alcohol acetate, can be improved, the use of the conductive paste for MLCC can suppress the generation of aggregated particles. The debonding agent is also excellent in the manufacturing steps of the MLCC. Thereby, it is possible to contribute to the manufacture of MLCCs with short circuits and less delamination.

圖1為比較實施例1~4及比較例1~3所得到的鎳粉於1385cm-1之吸光度Ia與於1600cm-1之吸光度Ib的比(Ib/Ia)之圖。 Comparative Example 1 is 1 to 4 and Comparative Examples 1 to 3, the nickel powder obtained in the absorbance at 1385cm -1 I a ratio of absorbance at 1600cm -1 I b of (I b / I a) of the embodiment of FIG.

用以實施發明之形態Form for implementing the invention [鎳粉]  [nickel powder]  

本發明之鎳粉中，包含有依照各種製造方法所製造的鎳粉與以鎳為主成分之鎳合金粉。就鎳合金粉而言，係為了賦予抗氧化性等、提升導電率，有對鎳添加鉻、矽、硼、磷、稀土族元素、貴金屬元素等而成的合金粉。 The nickel powder of the present invention contains nickel powder produced by various production methods and nickel alloy powder containing nickel as a main component. In order to impart oxidation resistance and the like, the nickel alloy powder is an alloy powder obtained by adding chromium, niobium, boron, phosphorus, a rare earth element, or a noble metal element to nickel.

本發明之鎳粉的數量平均粒徑為1μm以下。較佳為數量平均粒徑為0.4μm以下，更佳為0.25μm以下。本發明之鎳粉的數量平均粒徑的下限沒有特別限制，從一般的鎳粉之生產成本、用途的觀點來看，較佳為0.01μm以上。 The nickel powder of the present invention has a number average particle diameter of 1 μm or less. The number average particle diameter is preferably 0.4 μm or less, more preferably 0.25 μm or less. The lower limit of the number average particle diameter of the nickel powder of the present invention is not particularly limited, and is preferably 0.01 μm or more from the viewpoint of the production cost and use of the general nickel powder.

另外，本發明之鎳粉的微晶直徑為大於40nm。本發明的微晶直徑d係對(111)面進行X射線繞射測定，用謝樂方程式(Scherrer equation)(式2)計算而得。其中，K為謝樂常數、λ為測定X射線波長、β為半值寬(half value width)、θ為繞射角。藉由微晶直徑d數值高，則於MLCC的製造步驟會有良好的燒結性。 Further, the nickel powder of the present invention has a crystallite diameter of more than 40 nm. The crystallite diameter d of the present invention is obtained by X-ray diffraction measurement of the (111) plane, and is calculated by the Scherrer equation (Formula 2). Where K is the Xerox constant, λ is the measured X-ray wavelength, β is the half value width, and θ is the diffraction angle. By the high value of the crystallite diameter d, there is good sinterability in the manufacturing step of the MLCC.

本發明之鎳粉的數量平均粒徑係以掃描電子顯微鏡拍攝鎳粉的一次粒子的照片，使用圖像分析軟體從該照片測定500個以上粒子的粒徑，由所得到的鎳粉之粒度分布，算出其數量平均粒徑。此時，粒徑為包圍粒子的最小圓之直徑。 The number average particle diameter of the nickel powder of the present invention is a photograph of primary particles of nickel powder taken by a scanning electron microscope, and the particle size of 500 or more particles is measured from the photograph using an image analysis software, and the particle size distribution of the obtained nickel powder is obtained. Calculate the number average particle size. At this time, the particle diameter is the diameter of the smallest circle surrounding the particles.

本發明之鎳粉的形狀較佳為球狀。本發明之球狀係指縱橫比為1.2以下、圓度係數為0.675以上。縱橫比為包圍粒子的最小橢圓的長徑與短徑的比。而圓度係數為將包圍粒子的最小橢圓的面積設為S、周長設為L時，以4πS‧L-2來定義之值。鎳的形狀為球狀，藉此於MLCC的內部電極加工時，充填率變高且平坦性變好，可抑制龜裂與分層。 The shape of the nickel powder of the present invention is preferably spherical. The spherical shape of the present invention means that the aspect ratio is 1.2 or less and the circularity coefficient is 0.675 or more. The aspect ratio is the ratio of the major axis to the minor axis of the smallest ellipse surrounding the particle. The roundness coefficient is a value defined by 4πS‧L -2 when the area of the smallest ellipse surrounding the particle is S and the circumference is L. The shape of nickel is spherical, whereby the filling rate is increased and the flatness is improved when the internal electrode of the MLCC is processed, and cracking and delamination can be suppressed.

本發明之鎳粉以傅立葉轉換紅外光光度計測定時於1385cm-1之吸光度Ia與於1600cm-1之吸光度Ib的比(Ib/Ia)為0.8以上，碳濃度為0.05質量%以上2.0質量%以下。藉由將Ib/Ia設為0.8以上、碳濃度設為此範圍，可得到去黏結劑性、對低極性溶劑的潤濕性優異之 鎳粉。碳濃度較佳為0.1質量%以上1.0質量%以下，更佳為0.2質量%以上0.8質量%以下。 Nickel powder of the present invention, the absorbance at 1385cm -1 in the Fourier transform of the ratio I a to I b of 1600cm -1 absorbance of infrared light photometer (I b / I a) is 0.8 or more, a carbon concentration of 0.05 mass% 2.0% by mass or less. By setting I b /I a to 0.8 or more and the carbon concentration to be in this range, it is possible to obtain a nickel powder which is excellent in debonding property and wettability to a low polar solvent. The carbon concentration is preferably 0.1% by mass or more and 1.0% by mass or less, more preferably 0.2% by mass or more and 0.8% by mass or less.

又，本發明之鎳粉較佳為表面被親水親油平衡值(HLB)為11以下且分解溫度為300℃以下之單羧酸被覆。特別是從優異的去黏結劑性、優異的對低極性溶劑的潤濕性、優異的分散性的觀點來看，單羧酸較佳為HLB為1以上11以下，更佳為HLB為5以上8以下之單羧酸(R-COOH)。單羧酸的R分子構造為鏈狀或環狀任一者皆可。具體而言，可列舉直鏈狀或分枝狀烷基、乙烯基、烯丙基、芳烷基、環烷基、芳基。 Further, the nickel powder of the present invention preferably has a surface coated with a monocarboxylic acid having a hydrophilic-lipophilic balance (HLB) of 11 or less and a decomposition temperature of 300 ° C or lower. In particular, from the viewpoints of excellent debonding property, excellent wettability to a low-polar solvent, and excellent dispersibility, the monocarboxylic acid preferably has an HLB of 1 or more and 11 or less, more preferably an HLB of 5 or more. A monocarboxylic acid (R-COOH) of 8 or less. The R molecule of the monocarboxylic acid may be in the form of a chain or a ring. Specific examples thereof include a linear or branched alkyl group, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group, and an aryl group.

作為HLB為11以下的單羧酸可列舉，選自例如丁酸(HLB=10.2)、戊酸(HLB=8.8)、己酸(HLB=7.7)、庚酸(HLB=6.9)、辛酸(HLB=6.2)、壬酸(HLB=5.7)、癸酸(HLB=5.2)、苯甲酸(HLB=7.4)、環己烷甲酸(HLB=7.0)、對甲苯甲酸(HLB=6.6)中之至少1個的單羧酸。若考量作業性，較佳為癸酸、苯甲酸。 Examples of the monocarboxylic acid having an HLB of 11 or less include, for example, butyric acid (HLB = 10.2), valeric acid (HLB = 8.8), hexanoic acid (HLB = 7.7), heptanoic acid (HLB = 6.9), and octanoic acid (HLB). =6.2), at least 1 of decanoic acid (HLB=5.7), citric acid (HLB=5.2), benzoic acid (HLB=7.4), cyclohexanecarboxylic acid (HLB=7.0), p-toluic acid (HLB=6.6) Monocarboxylic acids. When considering workability, it is preferably citric acid or benzoic acid.

又，本發明之鎳粉較佳為鈉濃度為0.001質量%以下，鈣濃度為0.001質量%以下。鈉及鈣因有會與MLCC的介電體材料反應並使MLCC的容量降低等問題，所以期望不含有。鈉及鈣的有無，可透過例如感應耦合電漿質量分析來作確認。 Further, the nickel powder of the present invention preferably has a sodium concentration of 0.001% by mass or less and a calcium concentration of 0.001% by mass or less. Since sodium and calcium have problems such as reaction with a dielectric material of MLCC and a decrease in the capacity of MLCC, it is desirable not to contain it. The presence or absence of sodium and calcium can be confirmed by, for example, inductively coupled plasma mass analysis.

再者，本發明之鎳粉亦可含有0.01質量%~5.0質量%的硫。藉由將硫濃度設定在此範圍，可改善燒結行為。鎳粉中之硫濃度較佳為0.01質量%~1.0質量%，更佳為0.02質量%~0.2質量%。特別是鎳的表面被硫或硫酸基被覆者為佳。 Further, the nickel powder of the present invention may contain 0.01% by mass to 5.0% by mass of sulfur. By setting the sulfur concentration within this range, the sintering behavior can be improved. The sulfur concentration in the nickel powder is preferably from 0.01% by mass to 1.0% by mass, more preferably from 0.02% by mass to 0.2% by mass. In particular, it is preferred that the surface of the nickel is coated with sulfur or a sulfate group.

藉由成為上述構成，本發明之鎳粉可成為對於低極性溶劑為優異的鎳粉，該鎳粉係在混合鎳粉與二氫萜品醇乙酸酯時，以鎳粉的每表面積(m-2)的二氫萜品醇乙酸酯之添加量(g)為0.02g‧m2以下成為糊狀。具體而言，糊狀的評價方法，係將1g預先測定比表面積的試料鋪在玻璃板上，在以玻璃吸管滴下二氫萜品醇乙酸酯(Nippon Terpene Chemicals,Inc.製，純度95%，HLB=0)之後，以刮鏟充分混練，重複直至變成糊狀為止，求得所需要的二氫萜品醇乙酸酯之添加量，求得鎳粉的每表面積的二氫萜品醇乙酸酯之添加量。此處所謂的糊狀係指將載有試料的玻璃板垂直傾斜保持10秒鐘時，試料的95%以上仍保持附著於玻璃板上的狀態。又，比表面積是將試料以200℃進行30分鐘脫氣處理後，以BET法測量的比表面積。 By the above configuration, the nickel powder of the present invention can be an excellent nickel powder for a low-polarity solvent, and the nickel powder is used as a surface area of nickel powder when the nickel powder and the dihydroterpene alcohol acetate are mixed. The addition amount (g) of dihydroterpene alcohol acetate of -2 ) is 0.02 g ‧ m 2 or less and becomes a paste. Specifically, in the paste evaluation method, 1 g of a sample having a specific surface area measured in advance was placed on a glass plate, and dihydroterpineol acetate (Nippon Terpene Chemicals, Inc., manufactured by Nippon Terpene Chemicals, Inc., purity 95%) was dropped on a glass pipette. After HLB=0), the mixture was thoroughly kneaded with a spatula and repeated until it became a paste. The amount of dihydroterpineol acetate added was determined to determine the dihydroterpineol per surface area of the nickel powder. The amount of acetate added. Here, the paste state means that when the glass plate carrying the sample is vertically tilted for 10 seconds, 95% or more of the sample remains adhered to the glass plate. Further, the specific surface area is a specific surface area measured by the BET method after the sample was subjected to deaeration treatment at 200 ° C for 30 minutes.

此外，本發明之鎳粉亦為對低極性溶劑分散性優異的鎳粉，該鎳粉係於二氫萜品醇乙酸酯中於雷射繞射式濕式粒度分布測定時之累積體積頻率為75%粒徑為2.3μm以下。雷射繞射式濕式粒度分布測定所得到的粒度分布，顯示比以電子顯微鏡所觀察的一次粒子的粒度分布更大的值。這是因為雷射繞射式濕式粒度分布測定係於二氫萜品醇乙酸酯中測定凝集之凝集體的粒度分布之故。具體而言，雷射繞射式濕式粒度分布測定方法係於燒杯中秤量0.2g的試料，添加20ml的二氫萜品醇乙酸酯後，以超音波洗淨槽(AS ONE股份有限公司製，USK-1A)進行5min的分散處理。另一方面，於雷射繞射 式濕式粒度分布測定機(Beckman Coulter股份有限公司製、LS-230)的流通槽內以二氫萜品醇乙酸酯裝滿，試料分散處理後，將試料導入雷射繞射式粒度分布測定機中，測定粒度分布。 In addition, the nickel powder of the present invention is also a nickel powder excellent in dispersibility for a low-polar solvent, and the nickel powder is used in dihydroterpene alcohol acetate to accumulate volume frequency in laser diffraction type wet particle size distribution measurement. The particle size of 75% is 2.3 μm or less. The particle size distribution obtained by the laser diffraction type wet particle size distribution measurement showed a larger value than the particle size distribution of the primary particles observed by an electron microscope. This is because the laser diffraction type wet particle size distribution measurement determines the particle size distribution of the aggregated aggregate in dihydroterpene alcohol acetate. Specifically, the laser diffraction type wet particle size distribution measuring method is to measure 0.2 g of the sample in a beaker, and after adding 20 ml of dihydrofurfuryl alcohol acetate, the ultrasonic cleaning tank (AS ONE Co., Ltd.) System, USK-1A) was subjected to a dispersion treatment for 5 minutes. On the other hand, in a flow cell of a laser diffraction type wet particle size distribution measuring machine (Beckman Coulter Co., Ltd., LS-230), it is filled with dihydrofurfuryl alcohol acetate, and after the sample is dispersed, The sample was introduced into a laser diffraction type particle size distribution measuring machine to measure the particle size distribution.

此外，本發明之鎳粉係可成為於非活性環境下以300℃進行熱處理時的碳濃度之減少率為50%以上且去黏結劑性優異的鎳粉。具體來說，碳濃度之減少率的測定方法係指將約2g的試料放置於氧化鋁板上，放入石墨管式氣體環境電爐(Tamman tube type atmospheric electric furnace)(MOTOYAMA股份有限公司製，SUPER BURN SLT2035D)，一邊讓氬氣以1.0L/min流通於爐內，一邊進行升降溫速度2℃/min、最高溫度300℃、在最高溫度的保持時間1h之熱處理，而熱處理前後的碳濃度之減少率((1-熱處理前的碳濃度/熱處理後的碳濃度)×100%)為50%以上。 Further, the nickel powder of the present invention can be a nickel powder having a carbon concentration reduction rate of 50% or more and excellent debonding property when heat-treated at 300 ° C in an inert atmosphere. Specifically, the method for measuring the reduction rate of the carbon concentration means that about 2 g of the sample is placed on an alumina plate and placed in a Tamman tube type atmospheric electric furnace (MOTOYAMA Co., Ltd., SUPER BURN). SLT2035D), while allowing argon gas to flow into the furnace at 1.0 L/min, heat treatment at a temperature rise and fall rate of 2 ° C / min, a maximum temperature of 300 ° C, and a holding time of the highest temperature for 1 h, and reduction of carbon concentration before and after heat treatment The rate ((1 - carbon concentration before heat treatment / carbon concentration after heat treatment) x 100%) is 50% or more.

[鎳粉之製造方法]  [Method of manufacturing nickel powder]  

本發明之鎳粉可以例如氣相法或液相法等已知方法來製造。就能容易地控制生成的金屬微粉末之粒徑，更進一步能有效率地製造球狀粒子的觀點來說，特別是藉由讓氯化鎳氣體與還原性氣體接觸而產生鎳粉之氣相還原法，或將熱分解性的鎳化合物噴霧並熱分解之噴霧熱分解法較佳。從能精密控制生成的鎳粉之粒徑，進一步能防止粗大粒子的產生的觀點來看，特別是藉由讓氯化鎳氣體與還原性氣體接觸來進行之氣相還原法較佳。 The nickel powder of the present invention can be produced by a known method such as a vapor phase method or a liquid phase method. The particle size of the produced metal micropowder can be easily controlled, and the viewpoint of efficiently producing spherical particles can be produced, in particular, by bringing nickel chloride gas into contact with a reducing gas to produce a vapor phase of nickel powder. A reduction method or a spray pyrolysis method in which a thermally decomposable nickel compound is sprayed and thermally decomposed is preferred. From the viewpoint of further controlling the particle diameter of the produced nickel powder and further preventing the generation of coarse particles, a gas phase reduction method in which nickel chloride gas is brought into contact with a reducing gas is preferable.

於氣相還原法中，係使被氣化的氯化鎳的氣體與氫等的還原性氣體進行反應。在此情形，也可加熱固態的氯化鎳使其蒸發，而生成氯化鎳氣體。然而，若考慮到防止氯化鎳的氧化或吸濕、及能量效率，則使氯氣接觸金屬鎳並連續地產生氯化鎳氣體，將此氯化鎳氣體直接供給至還原步驟，接著使其與還原性氣體接觸，將氯化鎳氣體連續地還原而製造鎳微粉末之方法為有利的。氣相還原法可高產率地得到微晶直徑d大於40nm的鎳粉。 In the vapor phase reduction method, a gas of vaporized nickel chloride is reacted with a reducing gas such as hydrogen. In this case, the solid nickel chloride can also be heated to evaporate to form nickel chloride gas. However, in consideration of prevention of oxidation or moisture absorption of nickel chloride and energy efficiency, chlorine gas is brought into contact with metallic nickel and nickel chloride gas is continuously generated, and this nickel chloride gas is directly supplied to a reduction step, followed by It is advantageous to contact the reducing gas to continuously reduce the nickel chloride gas to produce a nickel fine powder. The vapor phase reduction method can obtain a nickel powder having a crystallite diameter d of more than 40 nm in a high yield.

在使用於以鎳為主成分之合金粉末的製造方法之情形下之氯化鎳氣體以外的金屬氯化物氣體，可列舉出：三氯化矽(III)氣體、四氯化矽(IV)氣體、甲矽烷氣體、氯化銅(I)氣體、氯化銅(II)氣體、氯化銀氣體、氯化鉬(III)氣體、氯化鉬(V)氣體、氯化鐵(II)氣體、氯化鐵(III)氣體、氯化鉻(III)氣體、氯化鉻(VI)氣體、氯化鎢(II)氣體、氯化鎢(III)氣體、氯化鎢(IV)氣體、氯化鎢(V)氣體、氯化鎢(VI)氣體、氯化鉭(III)氣體、氯化鉭(V)氣體、氯化鈷氣體、氯化錸(III)氣體、氯化錸(IV)氣體、氯化錸(V)氣體、二硼烷氣體、膦氣體等及彼等的混合氣體。 Examples of the metal chloride gas other than the nickel chloride gas in the case of the method for producing an alloy powder containing nickel as a main component include ruthenium (III) chloride gas and ruthenium (IV) tetrachloride gas. , formoxane gas, copper (I) gas, copper (II) chloride gas, silver chloride gas, molybdenum(III) chloride gas, molybdenum chloride (V) gas, iron (II) chloride gas, Iron (III) chloride gas, chromium (III) chloride gas, chromium (VI) chloride gas, tungsten (II) chloride gas, tungsten (III) chloride gas, tungsten (IV) chloride gas, chlorination Tungsten (V) gas, tungsten (VI) chloride gas, cerium (III) chloride gas, cerium (V) chloride gas, cobalt chloride gas, cerium (III) chloride gas, cerium (IV) chloride gas , ruthenium chloride (V) gas, diborane gas, phosphine gas, etc. and a mixed gas thereof.

再者，還原性氣體可列舉出：氫氣、硫化氫氣體、氨氣、一氧化碳氣體、甲烷氣體及彼等的混合氣體。特佳為氫氣、硫化氫氣體、氨氣、及彼等的混合氣體。 Further, examples of the reducing gas include hydrogen gas, hydrogen sulfide gas, ammonia gas, carbon monoxide gas, methane gas, and a mixed gas thereof. Particularly preferred are hydrogen, hydrogen sulfide gas, ammonia, and a mixture thereof.

在由氣相還原反應而得的鎳粉之製造過程中，在氯化鎳氣體與還原性氣體接觸的瞬間，產生鎳原子，藉由鎳原子彼此碰撞‧凝集，鎳粒子產生並成長。於是，根據在還原步驟的氯化鎳氣體之分壓、溫度等的條件，決定所生成之鎳粉的粒徑。依據如上述的鎳粉之製造方法，由於產生因應於氯氣的供給量之量的氯化鎳氣體，藉由控制氯氣的供給量，可調整供給至還原步驟的氯化鎳氣體的量，藉此可控制所生成的鎳粉之粒徑。 In the production process of the nickel powder obtained by the vapor phase reduction reaction, nickel atoms are generated at the moment when the nickel chloride gas comes into contact with the reducing gas, and the nickel atoms collide with each other and aggregate, and the nickel particles are generated and grown. Then, the particle diameter of the produced nickel powder is determined according to the conditions of the partial pressure of the nickel chloride gas in the reduction step, the temperature, and the like. According to the method for producing a nickel powder as described above, the amount of the nickel chloride gas supplied to the reduction step can be adjusted by controlling the amount of chlorine gas supplied in accordance with the amount of chlorine gas supplied. The particle size of the produced nickel powder can be controlled.

此外，氯化鎳氣體由於是以氯氣與金屬的反應產生，故與藉由固態氯化鎳的加熱蒸發而產生氯化鎳氣體的方法不同，不僅能減少使用載體氣體，依照製造條件還可不使用載體氣體。因此，氣相還原反應的方面，藉由減少載體氣體的使用量及隨之的加熱能量的降低，可謀取製造成本的削減。 In addition, since the nickel chloride gas is produced by the reaction of chlorine gas with a metal, unlike the method of generating nickel chloride gas by heating and evaporation of solid nickel chloride, not only the use of the carrier gas but also the production conditions may not be used. Carrier gas. Therefore, in terms of the gas phase reduction reaction, the reduction in the production cost can be achieved by reducing the amount of the carrier gas used and the accompanying reduction in the heating energy.

又，藉由將非活性氣體混合至氯化步驟產生的氯化鎳氣體中，可控制還原步驟中的氯化鎳氣體之分壓。如此，藉由控制氯氣的供給量或供給至還原步驟之氯化鎳氣體的分壓，可控制鎳粉的粒徑，可抑制粒徑的變動，並可任意設定粒徑。 Further, by mixing the inert gas into the nickel chloride gas generated in the chlorination step, the partial pressure of the nickel chloride gas in the reduction step can be controlled. By controlling the supply amount of chlorine gas or the partial pressure of the nickel chloride gas supplied to the reduction step, the particle size of the nickel powder can be controlled, the fluctuation of the particle diameter can be suppressed, and the particle diameter can be arbitrarily set.

例如，起始原料之氯化鎳係使純度99.5%以上的粒狀、塊狀、板狀等的金屬鎳，先與氯氣反應而生成氯化鎳氣體。此時的溫度係為了充分進行反應而設為800℃以上且設為鎳的熔點1453℃以下。若考慮到反應速度與氯化爐的耐久性，實用上較佳為900℃~1100℃之範圍。 For example, the nickel chloride of the starting material is a nickel metal such as a granular, massive or plate-like metal having a purity of 99.5% or more, which is first reacted with chlorine gas to form a nickel chloride gas. The temperature at this time is set to 800 ° C or more in order to sufficiently carry out the reaction, and the melting point of nickel is 1453 ° C or less. Considering the reaction speed and the durability of the chlorination furnace, it is practically preferably in the range of 900 ° C to 1100 ° C.

接下來，將此氯化鎳氣體直接供給至還原步驟，使其與氫氣等的還原性氣體接觸反應。此時，以適當的氬、氮等的非活性氣體稀釋氯化鎳氣體，可控制氯化鎳氣體的分壓。藉由控制氯化鎳氣體的分壓，可控制於還原部生成的金屬粉末之粒度分布等的品質。藉此，可任意設定產生的金屬粉末的品質的同時，亦可使品質穩定。還原反應的溫度只要是足以使反應完成的溫度以上即可，較佳為鎳的熔點以下，若考慮到經濟性，則900℃~1100℃為實用的。 Next, this nickel chloride gas is directly supplied to a reduction step, and is brought into contact with a reducing gas such as hydrogen. At this time, the partial pressure of the nickel chloride gas can be controlled by diluting the nickel chloride gas with an inert gas such as argon or nitrogen. By controlling the partial pressure of the nickel chloride gas, it is possible to control the quality such as the particle size distribution of the metal powder produced in the reducing portion. Thereby, the quality of the produced metal powder can be arbitrarily set, and the quality can be stabilized. The temperature of the reduction reaction may be at least the temperature sufficient to complete the reaction, and is preferably not more than the melting point of nickel. From the viewpoint of economy, 900 ° C to 1100 ° C is practical.

生成如此進行還原反應之鎳粉後，將產生的鎳粉冷卻。冷卻時，為了防止因生成的鎳的一次粒子彼此凝集而產生二次粒子，並得到所期望的粒徑之鎳粉，期望藉由吹進氮氣等非活性氣體來將已終止還原反應的1000℃之氣流急速冷卻至400~800℃左右。然後，將產生的鎳粉藉由例如袋狀濾器等分離、回收。 After the nickel powder thus subjected to the reduction reaction is formed, the produced nickel powder is cooled. At the time of cooling, in order to prevent secondary particles from being generated by aggregation of primary particles of nickel which are generated, and to obtain nickel powder having a desired particle diameter, it is desirable to 1000 ° C which has terminated the reduction reaction by blowing an inert gas such as nitrogen. The airflow is rapidly cooled to about 400~800 °C. Then, the produced nickel powder is separated and recovered by, for example, a bag filter.

在由噴霧熱分解法而得的鎳粉之製造方法中，係以熱分解性的鎳化合物作為原料。具體而言，其包含硝酸鹽、硫酸鹽、鹼式硝酸鹽(oxynitrate)、鹼式硫酸鹽(oxysulfate)、氯化物、銨錯合物、磷酸鹽、羧酸鹽、烷氧化合物等中的1種或2種以上。將含有此鎳化合物之溶液噴霧，作成微細液滴。作為此時的溶劑，可使用水、醇、丙酮、醚等。又，噴霧之方法係藉由超音波或雙噴流噴嘴等的噴霧方法進行。將如此進行產生微細液滴，再以高溫加熱並將金屬化合物熱分解，而生成鎳粉。此時的加熱溫度係所使用的特定鎳化合物熱分解之溫度以上，較佳為金屬的熔點附近。 In the method for producing nickel powder obtained by the spray pyrolysis method, a thermally decomposable nickel compound is used as a raw material. Specifically, it comprises 1 of a nitrate, a sulfate, an oxynitrate, an oxysulfate, a chloride, an ammonium complex, a phosphate, a carboxylate, an alkoxide, or the like. Kind or more than two. A solution containing the nickel compound is sprayed to form fine droplets. As the solvent at this time, water, alcohol, acetone, ether or the like can be used. Further, the spraying method is carried out by a spraying method such as an ultrasonic wave or a double jet nozzle. The fine droplets are produced in this manner, and then heated at a high temperature to thermally decompose the metal compound to form nickel powder. The heating temperature at this time is preferably higher than the temperature at which the specific nickel compound used is thermally decomposed, and is preferably near the melting point of the metal.

由液相法而得的鎳粉之製造方法中，將含有硫酸鎳、氯化鎳或鎳錯合物之鎳水溶液，添加至氫氧化鈉等的鹼金屬氫氧化物中等，使其接觸並生成鎳氫氧化物，接下來以肼等的還原劑將鎳氫氧化物還原而得到金屬鎳粉。如此進行而生成的金屬鎳粉，為了得到均勻粒子視需要進行粉碎處理。 In the method for producing a nickel powder obtained by the liquid phase method, a nickel aqueous solution containing nickel sulfate, nickel chloride or a nickel complex is added to an alkali metal hydroxide such as sodium hydroxide to form a contact and generate The nickel hydroxide is then reduced with a reducing agent such as hydrazine to obtain a metallic nickel powder. The metallic nickel powder produced in this manner is pulverized as needed in order to obtain uniform particles.

依以上方法所得到的鎳粉，為了去除殘留的原料，較佳為將其分散於液相中，進行清洗。例如，將依以上方法所得到的鎳粉，以在pH、溫度經控制之特定條件，使其懸浮於碳酸水溶液中進行處理。藉由以碳酸水溶液處理，可充分去除附著於鎳粉表面上的氯等的雜質，同時因藉由存在於鎳粉表面上的氫氧化鎳等的氫氧化物、粒子彼此的摩擦等而自表面離開所形成的微粒被除去，可於表面形成均勻的氧化鎳之被膜。作為用碳酸水溶液之處理方法，可以是將鎳粉與碳酸水溶液混合之方法，或也可是將二氧化碳吹進經以純水清洗鎳粉後的水漿料中，或是將碳酸水溶液添加進經以純水清洗鎳粉後的水漿料中來處理。 The nickel powder obtained by the above method is preferably dispersed in a liquid phase for washing to remove residual raw materials. For example, the nickel powder obtained by the above method is suspended in an aqueous solution of carbonic acid under specific conditions controlled by pH and temperature. By treating with an aqueous solution of carbonic acid, impurities such as chlorine adhering to the surface of the nickel powder can be sufficiently removed, and the hydroxide or particles such as nickel hydroxide present on the surface of the nickel powder can be self-surfaced by friction or the like. The particles formed by the separation are removed, and a uniform film of nickel oxide can be formed on the surface. As a treatment method using an aqueous solution of carbonic acid, a method of mixing nickel powder with an aqueous solution of carbonic acid may be used, or carbon dioxide may be blown into a water slurry after washing nickel powder with pure water, or an aqueous solution of carbonic acid may be added thereto. The water slurry after washing the nickel powder with pure water is treated.

使本發明之鎳粉含有硫之方法，沒有特別限定，例如可採用以下方法。 The method of containing sulfur in the nickel powder of the present invention is not particularly limited, and for example, the following method can be employed.

(1)於上述還原反應中添加含硫氣體的方法 (1) A method of adding a sulfur-containing gas to the above reduction reaction

(2)將鎳粉與含硫氣體接觸處理的方法 (2) Method for contacting nickel powder with sulfur-containing gas

(3)以乾式混合鎳粉與固態之含硫化合物的方法 (3) Method for dry mixing nickel powder and solid sulfur compound

(4)將含硫化合物溶液添加至將鎳粉分散於液相中而成的漿料中的方法 (4) A method of adding a sulfur-containing compound solution to a slurry obtained by dispersing nickel powder in a liquid phase

(5)將含硫氣體吹泡至將鎳粉分散於液相中而成的漿料中的方法 (5) A method of blowing a sulfur-containing gas into a slurry obtained by dispersing nickel powder in a liquid phase

特別就可精密控制含硫量的觀點、可均勻添加硫的觀點來看，較佳為(1)及(4)之方法。於(1)、(2)、(5)之方法中所使用的含硫氣體沒有特別限定，可以是硫蒸氣、二氧化硫氣體、硫化氫氣體等，在還原步驟的溫度下為氣體之氣體，可直接或是稀釋而使用。其中，從在常溫為氣體而容易控制流量的觀點、混入雜質的可能性低的觀點來看，二氧化硫氣體及硫化氫氣體為有利的。 In particular, from the viewpoint of precise control of the sulfur content and the uniform addition of sulfur, the methods (1) and (4) are preferred. The sulfur-containing gas used in the methods (1), (2), and (5) is not particularly limited, and may be sulfur vapor, sulfur dioxide gas, hydrogen sulfide gas, or the like, and is a gas gas at a temperature of the reduction step. Use directly or diluted. Among them, sulfur dioxide gas and hydrogen sulfide gas are advantageous from the viewpoint of easily controlling the flow rate at a normal temperature as a gas and a low possibility of mixing impurities.

在前述的清洗步驟及加硫步驟後，將鎳粉漿料乾燥。乾燥方法沒有特別限定，可使用已知方法。具體來說，可列舉與高溫氣體接觸來乾燥之氣流乾燥、加熱乾燥、真空乾燥等。其中，氣流乾燥因不會有粒子彼此碰撞造成的含硫層之破壞而為較佳的。 After the aforementioned washing step and the vulcanization step, the nickel powder slurry is dried. The drying method is not particularly limited, and a known method can be used. Specifically, airflow drying, heat drying, vacuum drying, etc. which are dried by contact with a high temperature gas are mentioned. Among them, the air flow drying is preferable because the sulfur-containing layer is not damaged by collision of particles.

進一步，將如此進行所得到的鎳粉在浸漬於含有上述的親水親油平衡值(HLB)為11以下的單羧酸之溶液後，加以攪拌。 Further, the nickel powder thus obtained is immersed in a solution containing the above-mentioned monocarboxylic acid having a hydrophilic-lipophilic balance (HLB) of 11 or less, and then stirred.

含親水親油平衡值(HLB)為11以下的單羧酸之溶液的溶劑，可使用從純水、乙醇或工業用酒精或彼等之混合物中至少一種所選出的溶劑。特別是從鎳粉的分散容易性、經濟性的觀點來看，理想為使用純水。親水親油平衡值(HLB)為11以下的單羧酸係與上述的單羧酸相同。 A solvent containing a solution of a monocarboxylic acid having a hydrophilic-lipophilic balance (HLB) of 11 or less may be a solvent selected from at least one of pure water, ethanol or industrial alcohol or a mixture thereof. In particular, from the viewpoint of easiness of dispersion of nickel powder and economy, it is preferred to use pure water. The monocarboxylic acid having a hydrophilic-lipophilic balance (HLB) of 11 or less is the same as the above monocarboxylic acid.

此時，溶解於溶劑的上述單羧酸的量，也取決於之後添加的鎳粉的粒徑與所期望的分散性，而在數 量平均粒徑為100nm左右的鎳粉之情形，較佳的是相對於鎳粉為0.1~10質量%，較佳為0.2~2質量%。由於可充分得到鎳粉的對低極性溶劑的潤濕性及分散性之改善效果，降低乾燥後的碳濃度，故此範圍是較佳的。 In this case, the amount of the above monocarboxylic acid dissolved in the solvent is also preferably determined depending on the particle diameter of the nickel powder to be added and the desired dispersibility, and in the case of the nickel powder having a number average particle diameter of about 100 nm, preferably. It is 0.1 to 10% by mass, preferably 0.2 to 2% by mass, based on the nickel powder. Since the effect of improving the wettability and dispersibility of the low-polarity solvent of the nickel powder can be sufficiently obtained, and the carbon concentration after drying is lowered, the range is preferable.

又，溶劑的量，從分散的容易性、經濟性的觀點來看，較佳為將鎳粉的濃度調整成20~50質量%。 Further, the amount of the solvent is preferably adjusted to a concentration of the nickel powder of 20 to 50% by mass from the viewpoint of easiness of dispersion and economy.

攪拌時，較佳為使用濕式分散機使溶劑中的鎳粒子充分分散，在大於0℃且小於70℃之溫度範圍內，攪拌1分鐘至10小時，較佳為30分鐘至1小時。然後，將鎳粉漿料乾燥，得到本發明之鎳粉。 When stirring, it is preferred to sufficiently disperse the nickel particles in the solvent using a wet disperser, and to stir at a temperature of more than 0 ° C and less than 70 ° C for 1 minute to 10 hours, preferably 30 minutes to 1 hour. Then, the nickel powder slurry is dried to obtain the nickel powder of the present invention.

乾燥方法與在清洗步驟後，或是在清洗步驟及加硫步驟後的乾燥步驟相同。乾燥步驟沒有特別限制，可使用已知方法。具體而言，可列舉與高溫氣體接觸來乾燥之氣流乾燥、加熱乾燥、真空乾燥等。其中，氣流乾燥因不會有粒子彼此碰撞造成的含硫層之破壞而較佳。另外，也可視需要加入以噴射磨機等進行的粉碎處理。 The drying method is the same as the drying step after the washing step or after the washing step and the vulcanization step. The drying step is not particularly limited, and a known method can be used. Specifically, airflow drying, heat drying, vacuum drying, etc. which are dried by contact with a high temperature gas are mentioned. Among them, the airflow drying is preferred because the sulfur-containing layer is not damaged by collision of particles. Further, a pulverization treatment by a jet mill or the like may be added as needed.

然後，本發明之鎳粉可以例如添加萜品醇等的溶劑，視需要的乙基纖維素等的有機黏結劑、分散劑、及要塗布的陶瓷的未燒製粉，再以3枝輥混練之周知的方法，容易地製造高性能的鎳糊。作為溶劑，可列舉出：乙醇、丙酮、丙醇、乙酸乙酯、乙酸丁酯、***、石油醚、礦油精、其它石蠟系烴溶劑，或是丁基卡必醇、萜品醇、二氫萜品醇、丁基卡必醇乙酸酯、二氫萜品醇乙酸酯、乙酸二氫香芹酯(dihydrocarvyl acetate)、乙酸香 芹酯、乙酸松香酯、乙酸沉香酯等的乙酸酯系、或二氫萜品醇丙酸酯、丙酸二氫香芹酯、丙酸異莰酯等的丙酸酯系溶劑，乙賽路蘇或丁賽路蘇等的賽路蘇類、芳香族類、鄰苯二甲酸二乙酯等。 Then, the nickel powder of the present invention may be, for example, a solvent such as terpineol, an organic binder such as ethyl cellulose, a dispersant, and an unfired powder of a ceramic to be coated, and then kneaded by three rolls. A well-known method makes it easy to manufacture a high-performance nickel paste. Examples of the solvent include ethanol, acetone, propanol, ethyl acetate, butyl acetate, diethyl ether, petroleum ether, mineral spirits, and other paraffinic hydrocarbon solvents, or butyl carbitol, terpineol, and Acetic acid such as hydroquinone alcohol, butyl carbitol acetate, dihydroterpineol acetate, dihydrocarvyl acetate, celery acetate, rosin acetate, and acetal acetate a propionate-based solvent such as an ester system or a dihydrostilbene propionate, dihydrocarvyl propionate or isodecyl propionate, or a celecoxib such as a celecoxib or a dinosaurus. Aromatic, diethyl phthalate, etc.

而作為有機黏結劑，較佳為樹脂結合劑，可列舉例如乙基纖維素、聚乙烯縮醛、丙烯酸樹脂、酸醇樹脂等。 Further, as the organic binder, a resin binder is preferable, and examples thereof include ethyl cellulose, polyvinyl acetal, acrylic resin, and acid alcohol resin.

作為分散劑，能使用周知的適當者，例如可使用乙烯系聚合物、多元羧酸胺鹽、多元羧酸系等。 As the dispersing agent, a known one can be used. For example, a vinyl polymer, a polybasic carboxylic acid amine salt, a polyvalent carboxylic acid or the like can be used.

實施例Example

接下來，列舉實施例及比較例進一步具體說明本發明，但這僅單純為例示，並非限制本發明。 The present invention will be further described in detail by way of examples and comparative examples, but these are merely illustrative and not restrictive.

實施例與比較例之試料製作條件統整於表1。 The sample preparation conditions of the examples and the comparative examples are summarized in Table 1.

評價方法如下所述。 The evaluation method is as follows.

(1)一次粒徑  (1) Primary particle size  

以場發射掃描式電子顯微鏡(Hitachi High-Technologies股份有限公司製，S-4700)觀察試料， 以適當倍率拍攝粒子佔視野一整面之二次電子圖像。然後，對500個以上粒子進行影像分析，由包圍粒子的最小圓的直徑來計算粒度分布。另外，從平均縱橫比與平均圓度係數來評價粒子的形狀。 The sample was observed by a field emission scanning electron microscope (S-4700, manufactured by Hitachi High-Technologies Co., Ltd.), and a secondary electron image in which the particles occupied the entire surface of the field of view was imaged at an appropriate magnification. Then, image analysis was performed on more than 500 particles, and the particle size distribution was calculated from the diameter of the smallest circle surrounding the particles. Further, the shape of the particles was evaluated from the average aspect ratio and the average circularity coefficient.

(2)微晶直徑  (2) crystallite diameter  

以X射線繞射測定裝置(PANalytycal製，X’pert-MPD/PRO-MPD發散狹縫0.5°，無受光狹縫)，使用CuKα射線(波長λ=1.5418Å)，以管電壓45kV、管電流40mA、步進角0.02°、掃描速度0.04°/s之條件，對繞射角2θ=43.5~45.5°進行X射線繞射測定。以附屬的分析軟體(X‘pert High Score)檢測出對應於(111面)之44.5°附近的波峰位置θ並測定半值寬B，以謝樂常數K=0.9計使用謝樂方程式計算微晶直徑。 X-ray diffraction measuring device (manufactured by PANalytycal, X'pert-MPD/PRO-MPD divergence slit 0.5°, no light receiving slit), using CuKα ray (wavelength λ=1.5418Å), tube voltage 45kV, tube current X-ray diffraction measurement was performed on the diffraction angle 2θ=43.5 to 45.5° under conditions of 40 mA, a step angle of 0.02°, and a scanning speed of 0.04°/s. The peak position θ corresponding to the (111 plane) near 44.5° was detected by the attached analysis software (X'pert High Score) and the half value width B was measured, and the crystallite was calculated using the Scherrer equation by the Xerox constant K=0.9. diameter.

(3)比表面積  (3) specific surface area  

使用比表面積測定裝置(Yuasa Ionics股份有限公司製，Multisorb 16)，作為前處理係將裝有經秤量過的試料的測定槽***加熱包內，以200℃進行30分鐘脫氣處理後，放置冷卻至室溫。接著，使混合氣體(N2：30%、He：70%)流進測定槽，以液態氮冷卻槽部，使N2被吸附於試料表面後，將槽部回溫至常溫，使吸附的N2脫離，藉由熱傳導度檢測器測定其脫離過程之吸附氣體量，算出試料之BET比表面積。 Using a specific surface area measuring device (Multisorb 16 manufactured by Yuasa Ionics Co., Ltd.), a measuring tank equipped with the weighed sample was inserted into a heating bag as a pretreatment system, and degassed at 200 ° C for 30 minutes, and then placed and cooled. To room temperature. Next, a mixed gas (N 2 : 30%, He: 70%) is introduced into the measurement tank, and the groove portion is cooled by liquid nitrogen, and after N 2 is adsorbed on the surface of the sample, the groove portion is returned to normal temperature to cause adsorption. The N 2 was desorbed, and the amount of adsorbed gas in the detachment process was measured by a thermal conductivity detector to calculate the BET specific surface area of the sample.

(4)雜質濃度  (4) Impurity concentration  

以氟氫酸及硝酸分解0.1g的試料後，添加內標元素之溶液進行定容。然後，導入感應耦合電漿質譜儀(SII Nanotechnology Inc.製，SPQ9700)中，對鈉濃度與鈣濃度進行定量。 After dissolving 0.1 g of the sample with hydrofluoric acid and nitric acid, a solution of the internal standard element was added to carry out constant volume. Then, it was introduced into an inductively coupled plasma mass spectrometer (SPQ9700, manufactured by SII Nanotechnology Inc.) to quantify the sodium concentration and the calcium concentration.

(5)有機物之吸附狀態  (5) Adsorption state of organic matter  

以傅立葉轉換紅外光光度計(Thermo Fisher Scientific Inc.製，Nicolet 6700)測定紅外線吸收光譜後，使用附屬的分析軟體修正基線，檢測於1385cm-1之吸光度Ia與於1600cm-1之吸光度Ib的比(Ib/Ia)。由於在1600cm-1附近觀測到屬於羧酸陰離子之C=O不對稱振動(asymmetric stretching)的紅外吸光波峰，故暗示Ib/Ia高的試料含有羧酸系化合物。 Fourier transform infrared spectrophotometer (Thermo Fisher Scientific Inc., Ltd., Nicolet 6700) an infrared absorption spectrum was measured, using the attached analysis software baseline correction, absorbance detector at 1385cm -1 I a and the absorbance of the 1600cm I b -1 Ratio (I b /I a ). Since an infrared absorption peak of C=O asymmetric stretching belonging to a carboxylate anion was observed in the vicinity of 1600 cm -1 , it was suggested that the sample having a high I b /I a contained a carboxylic acid compound.

(6)碳濃度  (6) Carbon concentration  

將0.5g的試料放入氧化鋁坩鍋，使其在高頻爐氧氣流中燃燒。此時，藉由碳/硫分析裝置(堀場製作所股份有限公司製、EMIA-520SP)分析從試料中的碳所產生的二氧化碳，計算出碳濃度。 0.5 g of the sample was placed in an alumina crucible and burned in a high-frequency furnace oxygen stream. At this time, the carbon dioxide generated from the carbon in the sample was analyzed by a carbon/sulfur analyzer (manufactured by Horiba, Ltd., EMIA-520SP) to calculate the carbon concentration.

(7)去黏結劑性  (7) Debonding agent  

將約2g的試料放置於氧化鋁板上，放入石墨管式氣體環境電爐(Motoyama股份有限公司製，SUPER BURN SLT2035D)，一邊讓氬氣以1.0L/min流通於爐內， 一邊進行升降溫速度2℃/min、最高溫度300℃、在最高溫度的保持時間1h之熱處理，以上述方法測定碳濃度。藉由比較熱處理前後的碳濃度，評價去黏結劑性。熱處理所致的碳濃度之減少率((1-熱處理前的碳濃度/熱處理後的碳濃度)×100%)若為50%以上，則評價為良好(○)，若小於50%則評價為不良(×)。 About 2 g of the sample was placed on an alumina plate, and placed in a graphite tube type gas environment electric furnace (Super BURN SLT2035D, manufactured by Motoyama Co., Ltd.), and argon gas was circulated in the furnace at 1.0 L/min, and the temperature was raised and lowered. The carbon concentration was measured by the above method at a heat treatment of 2 ° C / min, a maximum temperature of 300 ° C, and a holding time of the highest temperature for 1 h. The debonding agent property was evaluated by comparing the carbon concentrations before and after the heat treatment. When the carbon concentration reduction rate by heat treatment ((1-carbon concentration before heat treatment/carbon concentration after heat treatment) × 100%) is 50% or more, it is evaluated as good (○), and if it is less than 50%, it is evaluated as Bad (×).

(8)對低極性溶劑的潤濕性  (8) Wettability to low polar solvents  

將1g預先測定比表面積的試料鋪在玻璃板上，以玻璃吸管滴下二氫萜品醇乙酸酯(Nippon Terpene Chemicals,Inc.製、純度95%、HLB=0)之後，以刮鏟充分混練，重複直到變成糊狀為止，求得所需要的二氫萜品醇乙酸酯之添加量。此處，所謂的糊狀係指將載有試料之玻璃板垂直傾斜保持10秒鐘時，試料的95%以上仍保持附著於玻璃板上的狀態。鎳粉之對低極性溶劑的潤濕性越高，到變成糊狀為止所需要的二氫萜品醇乙酸酯之添加量越少。變成糊狀為止所需的鎳粉的每表面積之二氫萜品醇乙酸酯的添加量為0.02g‧m-2以下的情形評價成良好(○)，大於0.02g‧m-2的情形評價成不良(×)。 1 g of the sample having a predetermined specific surface area was placed on a glass plate, and dihydroterpineol acetate (manufactured by Nippon Terpene Chemicals, Inc., purity: 95%, HLB = 0) was dropped by a glass pipette, and then thoroughly kneaded with a spatula. The mixture was repeated until it became a paste, and the amount of dihydroterpineol acetate added was determined. Here, the paste form means that when the glass plate carrying the sample is vertically tilted for 10 seconds, 95% or more of the sample remains adhered to the glass plate. The higher the wettability of the nickel powder to the low-polarity solvent, the smaller the amount of dihydroterpineol acetate required to become a paste. When the amount of the dihydroterpene alcohol acetate per surface area of the nickel powder required to be a paste is 0.02 g·m -2 or less, it is evaluated as good (○), and more than 0.02 g ‧ m -2 Evaluation was poor (×).

(9)糊中的分散性  (9) Dispersibility in paste  

於燒杯中秤取0.2g的試料，添加20ml的二氫萜品醇乙酸酯後，以超音波清洗槽(AS ONE股份有限公司製，USK-1A)進行5min分散處理。另一方面，於雷射繞射式濕式粒度分布測定機(Beckman Coulter股份有 限公司製，LS-230)的流通槽內以二氫萜品醇乙酸酯裝滿。在試料的分散處理後，以玻璃吸管適量採取試料，導入雷射繞射式粒度分布測定機中，測定粒度分布。如此進行所得到的粒度分布雖然顯示出比以電子顯微鏡觀察到的一次粒子之粒度分布還要大的值，但這是因為就雷射繞射式濕式粒度分布測定而言，其係測定於二氫萜品醇乙酸酯中粒子凝集而成之凝集體的粒度分布之故。粒度分布的D25、D50、D75分別意指累積體積頻率為25%、50%、75%的粒徑。在糊中分散性越好的試料，則凝集體的粒度變得越小。D75若為2.3μm以下，則評價為良好(○)，大於2.3，則評價為不良(×)。 0.2 g of the sample was weighed in a beaker, and 20 ml of dihydroterpineol acetate was added thereto, and then subjected to dispersion treatment for 5 minutes in an ultrasonic cleaning tank (USK-1A, manufactured by AS ONE Co., Ltd.). On the other hand, in a flow cell of a laser diffraction type wet particle size distribution measuring machine (LS-230, manufactured by Beckman Coulter Co., Ltd.), it was filled with dihydroterpineol acetate. After the dispersion treatment of the sample, a sample was taken in an appropriate amount in a glass pipette, and introduced into a laser diffraction type particle size distribution measuring machine to measure the particle size distribution. The particle size distribution thus obtained shows a larger value than the particle size distribution of the primary particles observed by an electron microscope, but this is because the laser diffraction type particle size distribution measurement is measured by The particle size distribution of the aggregate formed by the agglomeration of the particles in the dihydroterpene alcohol acetate. D25, D50, and D75 of the particle size distribution mean particle diameters of cumulative volume frequencies of 25%, 50%, and 75%, respectively. The better the dispersibility in the paste, the smaller the particle size of the aggregate becomes. When D75 is 2.3 μm or less, it is evaluated as good (○), and when it is more than 2.3, it is evaluated as defective (×).

(實施例1)  (Example 1)  

在使氯化鎳與氫氣反應之氣相反應法後，在純水中及碳酸水溶液中進行洗淨，加以乾燥、粉碎，來備製鎳粉。以電子顯微鏡對此鎳粉進行評價，確認其為數量平均粒徑為110nm、平均縱橫比為0.85、平均圓度係數為1.09的球狀鎳粉。另外，從X射線繞射測定的結果來看，微晶直徑d為54.7nm。比表面積為6.42m2‧g-1。雜質濃度為鈉濃度小於0.001質量%，鈣濃度小於0.001質量%。 After the gas phase reaction method in which nickel chloride and hydrogen are reacted, the mixture is washed in pure water and an aqueous solution of carbonic acid, dried, and pulverized to prepare a nickel powder. The nickel powder was evaluated by an electron microscope to confirm that it was a spherical nickel powder having a number average particle diameter of 110 nm, an average aspect ratio of 0.85, and an average circularity coefficient of 1.09. Further, from the results of the X-ray diffraction measurement, the crystallite diameter d was 54.7 nm. The specific surface area is 6.42 m 2 ‧ g -1 . The impurity concentration is a sodium concentration of less than 0.001% by mass and a calcium concentration of less than 0.001% by mass.

以相對於鎳粉之濃度為0.25質量%之方式，在燒瓶中秤量苯甲酸(關東化學股份有限公司製，特級，HLB=7.4)，對上述鎳粉添加純水，用攪拌機以100rpm×30min攪拌後，加以溶解，調製鎳粉分散液。 The benzoic acid (manufactured by Kanto Chemical Co., Ltd., special grade, HLB=7.4) was weighed in a flask so that the concentration of the nickel powder was 0.25 mass%, pure water was added to the above nickel powder, and stirred at 100 rpm x 30 min with a stirrer. Thereafter, it was dissolved to prepare a nickel powder dispersion.

然後，一邊使氮氣以約100ml/min流通於燒瓶的空隙，一邊以油浴加熱燒瓶的底部至100℃，使水分揮發。冷卻至室溫後，回收鎳粉，以250μm的尼龍篩網過篩，當作為試料。 Then, while flowing nitrogen gas to the gap of the flask at about 100 ml/min, the bottom of the flask was heated to 100 ° C in an oil bath to volatilize the water. After cooling to room temperature, nickel powder was recovered and sieved through a 250 μm nylon mesh as a sample.

(實施例2)  (Example 2)  

除了將苯甲酸的量變更為0.5質量%以外，與實施例1同樣地製作試料，進行評價。 A sample was prepared and evaluated in the same manner as in Example 1 except that the amount of benzoic acid was changed to 0.5% by mass.

(實施例3)  (Example 3)  

除了將苯甲酸的量變更為1質量%以外，與實施例1同樣地製作試料，進行評價。 A sample was prepared and evaluated in the same manner as in Example 1 except that the amount of benzoic acid was changed to 1% by mass.

(實施例4)  (Example 4)  

除了將苯甲酸變更為正癸酸(關東化學股份有限公司製，鹿(CICA：C hemicals I ndustrial products C ollect A ssociate)1級，HLB=5.2)1質量%、純水變更為乙醇、油浴的加熱溫度變更為80℃以外，與實施例1同樣地製作試料，進行評價。 In addition to the conversion of benzoic acid to n-decanoic acid (manufactured by Kanto Chemical Co., Ltd., deer (CICA: C hemicals I sinustrial products C ollect A ssociate ) grade 1, HLB = 5.2) 1% by mass, pure water was changed to ethanol, oil bath A sample was prepared and evaluated in the same manner as in Example 1 except that the heating temperature was changed to 80 °C.

(比較例1)  (Comparative Example 1)  

除了將實施例1的苯甲酸變更為乙酸(關東化學股份有限公司製，特級，HLB=15.0)1質量%以外，與實施例1同樣地製作試料，進行評價。 A sample was prepared and evaluated in the same manner as in Example 1 except that the benzoic acid of Example 1 was changed to 1% by mass of acetic acid (manufactured by Kanto Chemical Co., Ltd., special grade, HLB = 15.0).

(比較例2)  (Comparative Example 2)  

除了將實施例4的正癸酸變更為市售的多元羧酸系分散劑(Croda Japan KK製，Hypermer KD-9，HLB<9)以外，與實施例4同樣地製作試料，進行評價。 A sample was prepared and evaluated in the same manner as in Example 4 except that the n-decanoic acid of Example 4 was changed to a commercially available polycarboxylic acid-based dispersant (manufactured by Croda Japan KK, Hypermer KD-9, HLB<9).

(比較例3)  (Comparative Example 3)  

針對沒有添加在實施例1所準備的有機物之鎳粉，進行與實施例1相同的評價。 The same evaluation as in Example 1 was carried out for the nickel powder to which the organic substance prepared in Example 1 was not added.

對實施例1~4、比較例1~3中所得到的試料，評價其有機物的吸附狀態、碳濃度‧去黏結劑性、對低極性溶劑的潤濕性、糊中之分散性。於圖1顯示有機物的吸附狀態之解析結果，於表2顯示碳濃度、去黏結劑性、對低極性溶劑的潤濕性、糊中之分散性的評價結果。 The samples obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated for their adsorption state, carbon concentration, debonding property, wettability to a low-polar solvent, and dispersibility in a paste. Fig. 1 shows the results of analysis of the adsorption state of the organic substance, and Table 2 shows the results of evaluation of the carbon concentration, the debonding agent property, the wettability to the low polar solvent, and the dispersibility in the paste.

根據圖1所示之紅外吸光光譜的解析結果，相較於沒有添加有機物的比較例3，添加有機物的實施例1~4及比較例1~2之Ib/Ia高，成為0.8以上，故暗示有羧酸系的有機物吸附。 According to the analysis result of the infrared absorption spectrum shown in FIG. 1, I b /I a of Examples 1 to 4 and Comparative Examples 1 and 2 in which organic substances were added was higher than Comparative Example 3 in which no organic substance was added, and was 0.8 or more. Therefore, it is suggested that there is adsorption of a carboxylic acid-based organic substance.

另外，由表2所示之碳濃度的分析結果可知，實施例1~4及比較例1、3與添加了市售的分散劑之比較例2相比，碳濃度更低。此外，因熱處理所致的碳濃度之減少率來看，可知實施例1~4及比較例1比起使用了市售的分散劑之比較例2，去黏結劑性也更為優異。實施例1~4及比較例1由於添加的有機物之分子量及分解溫度低，而被認為去黏結劑性優異。 Further, as a result of analysis of the carbon concentration shown in Table 2, it was found that Examples 1 to 4 and Comparative Examples 1 and 3 had a lower carbon concentration than Comparative Example 2 in which a commercially available dispersant was added. Further, in view of the reduction rate of the carbon concentration by the heat treatment, it was found that Examples 1 to 4 and Comparative Example 1 were superior in debonding property as compared with Comparative Example 2 using a commercially available dispersant. In Examples 1 to 4 and Comparative Example 1, since the added organic matter had a low molecular weight and a decomposition temperature, it was considered to be excellent in debonding property.

就對低極性溶劑的潤濕性之評價結果而言，相較於添加了HLB高的乙酸之比較例1及沒有添加有機物之比較例3，添加了HLB低的有機物之實施例1~4及比較例2，在變成糊狀為止所需的溶劑之添加量變少，由此可知對低極性溶劑的濕潤性優異。被認為藉由以HLB低的有機物被覆鎳粉，改善了潤濕性。 As a result of evaluating the wettability of the low-polarity solvent, Examples 1 to 4 in which an organic substance having a low HLB was added and Comparative Example 1 in which acetic acid having a high HLB was added and Comparative Example 3 in which no organic substance was added were added. In Comparative Example 2, the amount of the solvent required to be in a paste form was small, and it was found that the wettability to the low-polarity solvent was excellent. It is considered that the wettability is improved by coating the nickel powder with an organic substance having a low HLB.

就糊中的分散性評價結果而言，相較於添加了HLB高的乙酸之比較例1，及沒有添加有機物之比較例3，添加了HLB低的有機物之實施例1~4及比較例2，凝集體的粒度小，D75成為2.3μm以下，由此可知在糊中的分散性優異。這被認為是因為在實施例1~4及比較例2，由於對低極性溶劑的潤濕性被改善，所以在施以一定的分散力之情形變得容易分散的緣故。 As a result of the evaluation of the dispersibility in the paste, Comparative Examples 1 to which acetic acid having a high HLB was added, and Comparative Example 3 in which no organic substance was added, Examples 1 to 4 and Comparative Example 2 in which an organic substance having a low HLB was added were added. In addition, the particle size of the aggregate is small, and D75 is 2.3 μm or less, and thus it is understood that the dispersibility in the paste is excellent. This is considered to be because, in Examples 1 to 4 and Comparative Example 2, since the wettability to the low-polarity solvent was improved, it was easy to disperse when a certain dispersing force was applied.

實施例1~4由於添加的有機物為分解溫度與分子量低的單羧酸，所以去黏結劑性優異。而且因為所添加的有機物的HLB低，所以對低極性溶劑的潤濕性被改善，在糊中的分散性也被改善。 In Examples 1 to 4, since the organic substance to be added is a monocarboxylic acid having a decomposition temperature and a low molecular weight, the debonding property is excellent. Further, since the added organic matter has a low HLB, the wettability to the low-polar solvent is improved, and the dispersibility in the paste is also improved.

就比較例1而言，由於添加的有機物為分解溫度與分子量低的單羧酸，所以去黏結劑性優異。但因為添加的有機物的HLB高，對低極性溶劑的潤濕性不充分，其結果為在糊中的分散性也不充分。 In Comparative Example 1, since the organic substance to be added is a monocarboxylic acid having a decomposition temperature and a low molecular weight, the debonding property is excellent. However, since the added organic matter has a high HLB, the wettability to a low-polar solvent is insufficient, and as a result, the dispersibility in the paste is also insufficient.

就比較例2而言，由於添加的有機物的HLB低，所以對低極性溶劑的潤濕性與在糊中的分散性被改善。但是，由於所添加的有機物為分解溫度與分子量高的多元羧酸，所以去黏結劑性較本發明差。 In Comparative Example 2, since the added organic matter had a low HLB, the wettability to the low polar solvent and the dispersibility in the paste were improved. However, since the organic substance to be added is a polycarboxylic acid having a decomposition temperature and a high molecular weight, the debonding property is inferior to the present invention.

就比較例3而言，雖然因為沒有添加有機物而碳濃度低，但因鎳粉的表面覆蓋著親水性的氧化鎳，所以對低極性溶劑的潤濕性低，於糊中的分散性不良。 In Comparative Example 3, since the carbon concentration was low because no organic matter was added, since the surface of the nickel powder was covered with hydrophilic nickel oxide, the wettability to the low-polarity solvent was low, and the dispersibility in the paste was poor.

依據本發明，可提供添加的有機物之分解溫度與碳濃度為低的，有利於去黏結劑處理，對低極性溶劑特別是對二氫萜品醇乙酸酯的潤濕性及分散性被改善，適用於MLCC的製造之鎳粉及鎳糊。 According to the present invention, it is possible to provide a low decomposition temperature and a carbon concentration of the added organic substance, which is advantageous for the debonding agent treatment, and the wettability and dispersibility of the low polar solvent, particularly the dihydroterpene alcohol acetate, are improved. Suitable for nickel powder and nickel paste manufactured by MLCC.

Claims (8)

一種鎳粉，其係數量平均粒徑為1μm以下、微晶直徑d大於40nm的球狀鎳粉，其特徵在於以傅立葉轉換紅外光光度計(Fourier transform infrared spectrophotometer)測定時於1385cm -1之吸光度I a與於1600cm -1之吸光度I b的比(I b/I a)為0.8以上，碳濃度為0.05質量%以上2.0質量%以下，其中，微晶直徑d係對(111)面進行X射線繞射測定，用謝樂方程式(Scherrer equation)(式2)計算而得；K為謝樂常數，λ為測定X射線波長，β為半值寬(half value width)，θ為繞射角， A nickel powder having a spherical magnetic powder having a coefficient average particle diameter of 1 μm or less and a crystallite diameter d of more than 40 nm, which is characterized by an absorbance at 1385 cm -1 when measured by a Fourier transform infrared spectrophotometer (Fourier transform infrared spectrophotometer) I a ratio (I b / I a) in the absorbance at 1600cm -1 of I b is 0.8 or more, the carbon concentration less than 0.05 mass% 2.0 mass% or less, wherein, based on the crystallite diameter d (111) plane for X Ray diffraction measurement, calculated by Scherrer equation (Formula 2); K is the Xerox constant, λ is the X-ray wavelength, β is the half value width, and θ is the diffraction angle. , 如請求項1之鎳粉，其表面被親水親油平衡值(HLB)為11以下且分解溫度為300℃以下之單羧酸被覆。  The nickel powder of claim 1 is coated with a monocarboxylic acid having a hydrophilic-lipophilic balance (HLB) of 11 or less and a decomposition temperature of 300 ° C or less.   如請求項1或2之鎳粉，其鈉濃度為0.001質量%以下，鈣濃度為0.001質量%以下。  The nickel powder according to claim 1 or 2 has a sodium concentration of 0.001% by mass or less and a calcium concentration of 0.001% by mass or less.   如請求項1至3中任一項之鎳粉，其縱橫比為1.2以下，圓度係數為0.675以上。  The nickel powder according to any one of claims 1 to 3, which has an aspect ratio of 1.2 or less and a circularity coefficient of 0.675 or more.   如請求項1至4中任一項之鎳粉，其在非活性環境下以300℃進行熱處理時之碳濃度的減少率為50%以上。  The nickel powder according to any one of claims 1 to 4, which has a carbon concentration reduction rate of 50% or more when heat-treated at 300 ° C in an inert atmosphere.   如請求項1至5中任一項之鎳粉，其與二氫萜品醇乙酸酯混合時，鎳粉的每表面積的二氫萜品醇乙酸酯之添加量為0.02g‧m -2以下而成糊狀。 The nickel powder according to any one of claims 1 to 5, wherein, when mixed with the dihydroterpene alcohol acetate, the amount of the dihydroterpene alcohol acetate per surface area of the nickel powder is 0.02 g·m - 2 or less to form a paste. 如請求項1至6中任一項之鎳粉，其於二氫萜品醇乙酸酯中於雷射繞射式濕式粒度分布測定時之累積體積頻率為75%的粒徑為2.3μm以下。  The nickel powder according to any one of claims 1 to 6, which has a cumulative volume frequency of 75% and a particle diameter of 2.3 μm when measured in a laser diffraction type particle size distribution in dihydroterpene alcohol acetate. the following.   一種鎳糊，其特徵在於含有如請求項1至7中任一項之鎳粉。  A nickel paste characterized by containing the nickel powder of any one of claims 1 to 7.  
TW107107994A 2017-03-10 2018-03-09 Nickel powder and nickel paste TWI813559B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017045907 2017-03-10
JP2017-045907 2017-03-10

Publications (2)

Publication Number Publication Date
TW201842989A true TW201842989A (en) 2018-12-16
TWI813559B TWI813559B (en) 2023-09-01

Family

ID=63447678

Family Applications (1)

Application Number Title Priority Date Filing Date
TW107107994A TWI813559B (en) 2017-03-10 2018-03-09 Nickel powder and nickel paste

Country Status (5)

Country Link
JP (1) JP6425367B1 (en)
KR (1) KR102361800B1 (en)
CN (1) CN110461503B (en)
TW (1) TWI813559B (en)
WO (1) WO2018163823A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020066561A1 (en) * 2018-09-27 2020-04-02 富士フイルム株式会社 Polymer producing method, and a flow-type reaction system for producing polymer
JP7338529B2 (en) * 2020-03-24 2023-09-05 Tdk株式会社 Fluidizing particles and magnetic cores
TW202146114A (en) * 2020-04-14 2021-12-16 日商昭榮化學工業股份有限公司 Method for producing inorganic fine powder

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7261761B2 (en) * 2002-08-28 2007-08-28 Toho Titanium Co., Ltd. Metallic nickel powder and process for production thereof
JP3938770B2 (en) * 2004-04-16 2007-06-27 Ｔｄｋ株式会社 Nickel powder manufacturing method, nickel powder manufacturing device and nickel powder manufacturing crucible
EP1785207A4 (en) * 2004-06-16 2009-05-20 Toho Titanium Co Ltd Nickel powder and manufacturing method thereof
JP4207161B2 (en) * 2005-04-20 2009-01-14 セイコーエプソン株式会社 Microencapsulated metal particles and method for producing the same, aqueous dispersion, and ink jet ink
JP5299983B2 (en) * 2005-09-06 2013-09-25 株式会社三徳 Porous iron powder, method for producing porous iron powder, electromagnetic wave absorber
CN101600526A (en) * 2006-12-08 2009-12-09 东洋制罐株式会社 Make the ultrafine metal particle of microprotein inactivation
WO2009056401A1 (en) * 2007-09-27 2009-05-07 Basf Se Isolable and redispersable transition metal nanoparticles their preparation and use as ir absorbers
JP2010043345A (en) * 2008-08-18 2010-02-25 Sumitomo Electric Ind Ltd Nickel powder or alloy powder composed mainly of nickel and method for producing the same, conductive paste, and multilayer ceramic capacitor
JP5661273B2 (en) * 2008-11-26 2015-01-28 三ツ星ベルト株式会社 Colloidal metal particles, paste thereof and method for producing the same
JP5688895B2 (en) * 2008-12-26 2015-03-25 Ｄｏｗａエレクトロニクス株式会社 Fine silver particle powder and silver paste using the powder
JP5573083B2 (en) * 2009-10-01 2014-08-20 三洋電機株式会社 Hydrogen storage alloy electrode for alkaline storage battery
JP5523153B2 (en) * 2010-03-16 2014-06-18 Ｄｏｗａエレクトロニクス株式会社 Method for determination of benzotriazole on metal powder surface
JP2011214143A (en) 2010-03-17 2011-10-27 Nippon Steel Chem Co Ltd Method for production of nickel nanoparticle
CN102892533B (en) * 2010-03-17 2014-12-10 新日铁住金化学株式会社 Process for production of nickel nanoparticles
JP2011202265A (en) * 2010-03-26 2011-10-13 Dowa Electronics Materials Co Ltd Low temperature sinterable metal nanoparticle composition and electronic article formed using the composition
JP5245021B1 (en) * 2011-09-22 2013-07-24 株式会社日本触媒 Conductive fine particles and anisotropic conductive material containing the same
JP2013159830A (en) * 2012-02-06 2013-08-19 Toyota Central R&D Labs Inc Surface-coated metal nanoparticle, and method for producing the same
JP2013231230A (en) * 2012-04-04 2013-11-14 Nippon Steel & Sumikin Chemical Co Ltd Nickel composite particle
TWI597112B (en) * 2012-04-06 2017-09-01 東邦鈦股份有限公司 Nickel metal powder and process for production thereof
CN103692105A (en) * 2012-09-27 2014-04-02 旭化成电子材料株式会社 Device and method of solder cataplasm and semiconductor
WO2015012356A1 (en) * 2013-07-25 2015-01-29 石原産業株式会社 Metallic copper dispersion, method for manufacturing same, and usage for same
JP2015151558A (en) * 2014-02-12 2015-08-24 新日鉄住金化学株式会社 Nickel fine particle slurry, metal fine particle and method for producing the same
CN105900196B (en) * 2014-03-20 2017-09-05 积水化学工业株式会社 Conductive paste
KR102292897B1 (en) * 2014-04-08 2021-08-24 도호 티타늄 가부시키가이샤 Nickel powder
JP6685503B2 (en) * 2015-03-18 2020-04-22 株式会社リコー Three-dimensional modeling powder material, three-dimensional modeling kit, three-dimensional modeling green body, three-dimensional model and three-dimensional modeling green body manufacturing method, three-dimensional model and three-dimensional modeling green body manufacturing apparatus
CN104741603B (en) * 2015-04-11 2017-08-01 苏州大学 A kind of dissymmetrical structure Tri-metal nanoparticle, preparation method and applications
US10087504B2 (en) * 2015-08-13 2018-10-02 Samsung Electronics Co., Ltd. Semiconductor nanocrystals and method of preparation
JPWO2017056741A1 (en) * 2015-09-29 2018-07-19 東邦チタニウム株式会社 Nickel powder and nickel paste

Also Published As

Publication number Publication date
JPWO2018163823A1 (en) 2019-03-22
TWI813559B (en) 2023-09-01
JP6425367B1 (en) 2018-11-21
KR102361800B1 (en) 2022-02-10
KR20190123777A (en) 2019-11-01
CN110461503A (en) 2019-11-15
WO2018163823A1 (en) 2018-09-13
CN110461503B (en) 2022-01-14

Similar Documents

Publication Publication Date Title
KR101951452B1 (en) Coated metal microparticle and manufacturing method thereof
JP7042372B2 (en) Nickel powder and its manufacturing method, nickel paste
TWI716526B (en) Nickel powder
JP2016028176A (en) Method for manufacturing copper powder
TWI642626B (en) Method for manufacturing cuprous oxide particles, and method for manufacturing conductive film
KR20120038878A (en) Metal nanoparticles dispersion
JP2009120949A (en) Silver microparticle-containing composition, process for production of the composition, process for production of the silver microparticle, and paste containing the silver microparticle
JP6799936B2 (en) Nickel particles, conductive paste, internal electrodes and multilayer ceramic capacitors
JP6559118B2 (en) Nickel powder
JP5993764B2 (en) Composite nickel particles
TWI813559B (en) Nickel powder and nickel paste
JP3812359B2 (en) Method for producing metal powder
JP6539520B2 (en) Nickel fine particle containing composition and method for producing the same
JP2015049973A (en) Conductive paste and method for manufacturing composite nickel fine particle used therefor
JPWO2019146414A1 (en) Copper fine particles
JP2015151558A (en) Nickel fine particle slurry, metal fine particle and method for producing the same
JP4540364B2 (en) Nickel powder, and conductive paste and multilayer ceramic capacitor using the same
JP2020117433A (en) Glass particles, conductive composition therewith and production method of glass particles
WO2017179524A1 (en) Silver-coated copper powder and method for producing same
JP6799931B2 (en) Nickel fine particle-containing composition and its manufacturing method, internal electrodes and laminated ceramic capacitors
WO2020158685A1 (en) Sn particles, conductive composition using the same, and method for producing sn particles
TW202239980A (en) Nickel nanoparticles, paste materials, and laminated ceramic capacitors wherein the nickel nanoparticles have an average particle diameter of 5 nm to 100 nm and contain 99.5 parts by weight or more of a nickel component in 100 parts by weight of a metal component
CN115348907A (en) Copper particles and method for producing same
JP2013231229A (en) Nickel composite particle