TW201719678A - Nickel powder and nickel paste - Google Patents

Nickel powder and nickel paste Download PDF

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TW201719678A
TW201719678A TW105130714A TW105130714A TW201719678A TW 201719678 A TW201719678 A TW 201719678A TW 105130714 A TW105130714 A TW 105130714A TW 105130714 A TW105130714 A TW 105130714A TW 201719678 A TW201719678 A TW 201719678A
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nickel powder
nickel
less
mass
gas
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TWI701683B (en
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本多雄大
淺井剛
吉田貢
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東邦鈦股份有限公司
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    • 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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • 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
    • 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

Provided are a nickel powder and a nickel paste which are suitable as inner electrode materials for MLCCs and have excellent binder removability and improved wettability and dispersibility with and in low-polar solvents. A spherical nickel powder in which the number average particle diameter D of primary particles is 1 [mu]m or less. The spherical nickel powder has a sodium concentration of 0.001% by mass or less, a calcium concentration of 0.001% by mass or less and a carbon concentration of 0.05 to 2.0% by mass inclusive, has an infrared absorption peak at 1600 cm-1 as measured with a Fourier transform infrared spectrometer, can exert metallic luster when formed into a pasty form by kneading together with dihydroterpinylacetate, and has a rate of decrease in a carbon concentration of 50% or more when treated with heat at 300 DEG C under an inert atmosphere.

Description

鎳粉及鎳糊 Nickel powder and nickel paste

本發明關於適用於在電子零件等中使用之導電糊用途之鎳粉，特別是關於適合使用作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 for electronic parts and 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與平板終端裝置之電子機器中。 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 and a tablet terminal device.

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，來製作介電體生板(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」)，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，將其印刷於介電體生板上、乾燥。在將塗布了此電極層之介電體生板積層後，加熱加壓接著，形成積層體，加工成目標形狀。接下來，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「去除黏結劑處理」)，然後，在還原氣體環境中以1300℃左右的溫度燒成。最後，將外部電極鍍在積層體的外側 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 electrode paste. It is printed on a dielectric green plate and dried. After the dielectric layer coated with the electrode layer is laminated, it is heated and pressurized to form a layered body, which is processed into a target shape. Next, in order to remove the organic component such as the organic binder, the laminate is subjected to heat treatment in a weak oxidizing gas atmosphere (hereinafter referred to as "debonding treatment"), and then, at 1300 ° C in a reducing gas atmosphere. The left and right temperatures are fired. Finally, the external electrode is plated on the outside of the laminate. Get the MLCC on it.

近年來，伴隨著電子機器的小型化/高機能化，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。而過去雖係使用鈀等的貴金屬，但比較便宜的鎳等的卑金屬之使用也越來越多。 In recent years, with the miniaturization and high performance of electronic equipment, MLCC has also been developed toward miniaturization and large capacity, and thin film formation of internal electrode layers is required. 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 cheaper nickel such as nickel was increasing.

MLCC的內部電極用鎳粉，能藉由例如讓氯化鎳氣體與氫氣接觸之氣相反應法，以優良的生產率來合成平均粒徑為1.0μm以下且結晶性高的球狀鎳微粉。 In the internal electrode of the MLCC, nickel powder is used, and a spherical nickel fine powder having an average particle diameter of 1.0 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，會因短路與脫層而使MLCC的容量降低，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，脫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，為於燒成時內部電極層與介電體層剝離開來之結構缺陷。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 aggregates in the internal electrode paste, the capacity of the MLCC is lowered due to short-circuiting and 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 delamination is caused by insufficient aggregation of the nickel powder by 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 are formed at the time of firing. Structural defects in which the body layer is peeled off. Therefore, in order to produce an MLCC having a small structural defect and a small/large capacity, nickel powder having good dispersibility in the internal electrode paste is required.

為了提升鎳粉在內部電極糊中的分散性，提升對低極性溶媒的潤濕性為重要的。下式1稱為WASHBURN的算式，為關於粒子向溶媒中分散速度之理論式。其中，v為分散速度、η為溶媒黏度、L為細孔長度 、r為細孔半徑、γL為溶媒的表面張力、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，一方面顯示若對每個粒子與溶媒施加高分散壓力即能分散，另一方面顯示若潤濕性高，即使分散壓力變低也能分散。 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 polarity solvent. The following formula 1 is called the formula of WASHBURN and is a theoretical formula for the dispersion speed of particles into a solvent. Wherein v is a dispersion speed, η is a solvent viscosity, L is a pore length, r is a pore radius, γ L is a surface tension of a solvent, θ is a contact angle, and ΔP is a 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 each particle and the solvent are applied with a high dispersion pressure, it can be dispersed, and on the other hand, if the wettability is high, even if the dispersion pressure becomes low, it can be dispersed.

關於一次粒子的平均粒徑為1μm以下，且在糊中的分散性優良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產生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(例如參照日本國特開2011-214143公報)。 Regarding 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 having a nickel carboxylate and a primary amine is proposed. a first step of the mixture; heating the mixture to obtain a second step of producing a mis-formed reaction solution of 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 performed in a state in which a polyvalent carboxylic acid having a valence of 3 or more is present (for example, refer to JP-A-2011-214143 publication) ).

然而，上述文獻中所舉出的以多元羧酸處理之鎳粉，雖然改善了在低極性溶媒中的分散性，但關於對低極性溶媒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，不清楚是否有優良的分散性。 However, the nickel powder treated with the polycarboxylic acid as exemplified in the above literature improves the dispersibility in a low-polarity solvent, but does not mention at all about the wettability to a low-polarity 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，上述文獻中所舉出的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，必須在去除黏結劑步驟除去有機物，用高碳含有率且含有分解溫度高的有機物的金屬粉，於去除黏結劑處理不能完全去除有機物，而在接下去的燒成步驟中，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 mentioned in the above document has a high carbon content. As the metal powder used for the internal electrode of the MLCC, it is necessary to remove the organic matter in the step of removing the binder, and to use the metal powder having a high carbon content and containing an organic substance having a high decomposition temperature, the removal of the binder can not completely remove the organic matter, and the subsequent removal is performed. In the burning step, the residual The organic matter will become a gas, and as a result, it may become a cause of structural defects.

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，去除黏結劑性優良、對低極性溶媒的潤濕性及分散性已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 a nickel powder and a nickel paste which are suitable as an internal electrode material of MLCC and which have excellent adhesiveness and improved wettability and dispersibility for a low-polarity solvent.

本發明之鎳粉係一次粒子的數均粒徑D為1μm以下的球狀鎳粉，其特徵為：鈉濃度為0.001質量%以下、鈣濃度為0.001質量%以下、碳濃度為0.05質量%以上2.0質量%以下，以傅立葉轉換紅外線分光光度計測定時，在1600cm-1有紅外線吸光的吸收峰，與二氫萜品醇乙酸酯混練成為糊狀時，呈現金屬光澤，在惰性環境下以300℃進行熱處理時，碳濃度之減少率為50%以上。 The nickel powder of the present invention has a spherical nickel powder having a number average particle diameter D of 1 μm or less, and has a sodium concentration of 0.001% by mass or less, a calcium concentration of 0.001% by mass or less, and a carbon concentration of 0.05% by mass or more. 2.0% by mass or less, when measured by a Fourier transform infrared spectrophotometer, it has an absorption peak of infrared absorption at 1600 cm -1 , and when it is mixed with dihydroterpene alcohol acetate to form a paste, it exhibits metallic luster, and in an inert environment, 300 When the heat treatment is performed at ° C, the carbon concentration reduction rate is 50% or more.

依據本發明之鎳粉，因於MLCC的製造步驟中成為問題之雜質變少，能改善對低極性溶媒的潤濕性及分散性，故在使用作為MLCC用導電糊時，能抑制凝集粒子的產生，在MLCC的製造步驟中的去除黏結劑性也更佳。藉此，能有助於製造短路與脫層少的MLCC。 According to the nickel powder of the present invention, the impurities which are a problem in the production process of the MLCC are reduced, and the wettability and dispersibility to the low-polarity solvent can be improved. Therefore, when the conductive paste for MLCC is used, the aggregated particles can be suppressed. It is also preferable to remove the binder in the manufacturing step of the MLCC. Thereby, it is possible to contribute to the manufacture of MLCC with less short circuit and delamination.

第1圖為實施例1~4及比較例1~3所得到的鎳粉之紅外線吸收光譜。 Fig. 1 is an infrared absorption spectrum of nickel powders obtained in Examples 1 to 4 and Comparative Examples 1 to 3.

[實施發明之形態] [Formation of 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。鎳合金粉係為了賦予抗氧化性等與提升導電率，有對鎳添加鉻、矽、硼、磷與稀土類元素、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. 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 in order to impart oxidation resistance and the like.

本發明之鎳粉的數均粒徑為1.0μm以下。更佳為數均粒徑為0.4μm以下。本發明之鎳粉的數均粒徑的下限沒有特別限制，從通常的鎳粉之生產成本與用途之觀點來看，較佳為0.01μm以上。 The nickel powder of the present invention has a number average particle diameter of 1.0 μm or less. More preferably, the number average particle diameter is 0.4 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 usual nickel powder.

另外，本發明之鎳粉的數均粒徑D與微晶直徑d的比(d/D)較佳為0.40以上。本發明的微晶直徑d係對(111)面進行X射線繞射測定，用謝樂的算式(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d/D數值高，則於MLCC的製造步驟會有良好的燒結性。 Further, the ratio (d/D) of the number average particle diameter D of the nickel powder of the present invention to the crystallite diameter d is preferably 0.40 or more. The crystallite diameter d of the present invention is obtained by X-ray diffraction measurement of the (111) plane, and is calculated by Xie Le's formula (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 having a high d/D value, there is good sinterability in the manufacturing step of the MLCC.

本發明之鎳粉的數均粒徑係以掃描電子顯微鏡拍攝鎳粉的一次粒子的照片，從該照片使用圖像分析軟體測定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 the 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。而圓度係數為把包圍粒子的最小橢圓的面積設為S、周長設為L時，以 4πS/(L×L)來定義之值。藉由鎳的形狀為球狀，則於MLCC的內部電極加工時，充填率變高且平坦性變好，能抑制裂紋與脫層。 The nickel powder of the present invention has a spherical shape. 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 such that the area of the smallest ellipse surrounding the particle is S and the circumference is set to L. 4πS/(L×L) to define the value. When the shape of the nickel is spherical, the filling rate is increased and the flatness is improved during the internal electrode processing of the MLCC, and cracking and delamination can be suppressed.

本發明之鎳粉的鈉濃度為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讓MLCC的容量降低等問題，所以期望不含有。鈉及鈣的有無能透過例如感應耦合電漿質量分析來作確認。 The nickel powder of the present invention 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 reacting with a dielectric material of MLCC and lowering 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.

本發明之鎳粉，在以傅立葉轉換紅外線分光光度計測定時，於1600cm-1有紅外線吸光的吸收峰，碳濃度為0.05質量%以上2.0質量%以下。藉由在此範圍，能得到去除黏結劑性、對低極性溶媒的潤濕性優良之鎳粉。更佳為碳濃度為0.1質量%以上1.0質量%以下，再更佳為0.2質量%以上0.8質量%以下。 The nickel powder of the present invention has an absorption peak of infrared light absorption at 1600 cm -1 when measured by a Fourier transform infrared spectrophotometer, and the carbon concentration is 0.05% by mass or more and 2.0% by mass or less. Within this range, nickel powder excellent in debonding property and wettability to a low-polarity solvent can be obtained. More preferably, the carbon concentration is 0.1% by mass or more and 1.0% by mass or less, and more preferably 0.2% by mass or more and 0.8% by mass or less.

以傅立葉轉換紅外線分光光度計測定時在1600cm-1有紅外線吸光的吸收峰之鎳粉，能藉由以羧酸被覆鎳粉表面來達成。 The nickel powder having an absorption peak of infrared absorption at 1600 cm -1 when measured by a Fourier transform infrared spectrophotometer can be achieved by coating the surface of the nickel powder with a carboxylic acid.

本發明中優良的去除黏結劑性，係指在惰性環境下以300℃進行熱處理時的碳濃度之減少率為50%以上。具體來說，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(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的減少率((1-熱處理前的碳濃度/熱處理後 的碳濃度)×100%)為50%以上。 The excellent binder removal property in the present invention means that the carbon concentration reduction rate at the time of heat treatment at 300 ° C in an inert atmosphere is 50% or more. Specifically, about 2 g of the sample was placed on an alumina plate, and placed in a graphite tube type gas environment electric furnace (SUPERYAMA Co., Ltd., SUPER BURN SLT2035D), and argon gas was circulated in the furnace at 1.0 L/min. Heat treatment at a temperature of 2 ° C / min, a maximum temperature of 300 ° C, and a holding time of 1 h at the highest temperature, and a reduction rate of carbon concentration before and after heat treatment ((1 - carbon concentration before heat treatment / after heat treatment) The carbon concentration) × 100%) is 50% or more.

另外，本發明中，與二氫萜品醇乙酸酯混練成為糊狀時呈現金屬光澤這件事，係成為對低極性溶媒具有優良的潤濕性之指標。低極性溶媒係指HLB為5以下之溶媒，可列舉出例如：己烷、苯、甲苯、萜品醇、二氫萜品醇、二氫萜品醇乙酸酯等。 Further, in the present invention, when it is kneaded with dihydroterpene alcohol acetate to give a metallic luster, it is an index which has excellent wettability to a low-polarity solvent. The low-polarity solvent means a solvent having an HLB of 5 or less, and examples thereof include hexane, benzene, toluene, terpineol, dihydroterpineol, and dihydroterpineol acetate.

對低極性溶媒之潤濕性的評價方法，具體來說，係將1g的試料敷設於玻璃板上，一邊以滴管滴下二氫萜品醇乙酸酯(NIPPON TERPENE CHEMICALS Inc.製、純度95%、HLB=4.4)，一邊以調色刀充分混練，求取到成為糊狀為止所需要的二氫萜品醇乙酸酯的滴下量，並將所得到的糊以調色刀塗開，觀察表面。鎳粉對低極性溶媒之潤濕性越高，到成為糊狀為止所需要的二氫萜品醇乙酸酯的滴下量越少，所得到的糊呈現金屬光澤。在到成為糊狀為止的二氫萜品醇乙酸酯的滴下量為10滴以下且呈現金屬光澤的情形，即評價為具有優良的對低極性溶媒之潤濕性。 In the method of evaluating the wettability of the low-polarity solvent, specifically, 1 g of the sample was applied to a glass plate, and dihydroterpineol acetate (manufactured by NIPPON TERPENE CHEMICALS Inc., purity 95) was dropped by a dropper. %, HLB = 4.4), and thoroughly kneaded with a palette knife to obtain the amount of dihydroterpineol acetate required to be in a paste form, and the obtained paste was spread with a palette knife. Observe the surface. The higher the wettability of the nickel powder to the low-polarity solvent, the less the amount of dihydroterpineol acetate required to be in a paste form, and the resulting paste exhibits a metallic luster. The amount of dihydroterpineol acetate to be added to the paste was 10 drops or less and exhibited metallic luster, that is, it was evaluated to have excellent wettability to a low-polarity solvent.

本發明之鎳粉的較佳態樣係表面被親水親油平衡值(HLB)為11以下、分解溫度300℃以下的一元羧酸被覆著。本發明之鎳粉中，從優良的去除黏結劑性、優良的對低極性溶媒之潤濕性、優良的分散性之觀點來看，較佳的是上述羧酸係較佳為HLB在1以上11以下，更佳為HLB在3.5以上11以下之一元羧酸。一元羧酸的分子結構用直鏈狀或環狀中的任一種皆可。作為HLB為11以下的一元羧酸，可列舉出從下列之中所選出的至少一種一 元羧酸：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)、對甲苯甲酸(HLB=6.6)。若考慮作業性，較佳為癸酸、苯甲酸。 A preferred aspect of the nickel powder of the present invention 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. In the nickel powder of the present invention, from the viewpoint of excellent binder removal property, excellent wettability to a low-polarity solvent, and excellent dispersibility, it is preferred that the carboxylic acid is 1 or more HLB. 11 or less, more preferably one or more carboxylic acids having an HLB of 3.5 or more and 11 or less. The molecular structure of the monocarboxylic acid may be either linear or cyclic. The monocarboxylic acid having an HLB of 11 or less may, for example, be at least one selected from the group consisting of Metacarboxylic acid: butyric acid (HLB=10.2), valeric acid (HLB=8.8), hexanoic acid (HLB=7.7), heptanoic acid (HLB=6.9), octanoic acid (HLB=6.2), tannic acid (HLB=5.7) , citric acid (HLB = 5.2), benzoic acid (HLB = 7.4), p-toluic acid (HLB = 6.6). When considering workability, citric acid and benzoic acid are preferred.

又，本發明之鎳粉也可含有0.01質量%~5.0質量%的硫。藉由讓硫濃度在此範圍，能改善燒結行為。鎳粉中的硫濃度較佳為0.01質量%~1.0質量%，更佳為0.02質量%~0.2質量%。特佳為鎳的表面被硫或硫酸基被覆著。 Further, the nickel powder of the present invention may contain 0.01% by mass to 5.0% by mass of sulfur. By allowing the sulfur concentration to be in 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. Particularly preferred is the surface of nickel which is coated with sulfur or a sulfate group.

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

本發明之鎳粉能以例如氣相法或液相法等已知方法來製造。特別是藉由讓氯化鎳氣體與還原性氣體接觸來產生鎳粉之氣相還原法，或是將熱分解性的鎳化合物噴霧並熱分解之噴霧熱分解法，就能容易地控制產生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，較佳。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，從能精密控制產生的鎳粉之粒徑、進一步能防止粗大粒子的產生的觀點來看，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. In particular, it can be easily controlled by a vapor phase reduction method in which nickel chloride gas is brought into contact with a reducing gas to produce a nickel powder, or a spray pyrolysis method in which a thermally decomposable nickel compound is sprayed and thermally decomposed. The particle diameter of the metal fine powder is more preferable from the viewpoint of efficiently producing spherical particles. In particular, a gas phase reduction method in which nickel chloride gas is brought into contact with a reducing gas is preferred from the viewpoint of finely controlling the particle diameter of the nickel powder generated and further preventing the generation of coarse particles.

於氣相還原法中，係讓被氣化的氯化鎳的氣體與氫氣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，來產生氯化鎳氣體。然而，若考慮到氯化鎳的氧化或預防吸濕、及能量效率，則讓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，接下來使其與還原性氣體接 觸，將氯化鎳氣體連續地還原以製造鎳微粉末之方法為有利的。氣相還原法能以高產率得到數均粒徑D與微晶直徑d的比(d/D)為0.40以上之鎳粉。 In the vapor phase reduction method, a gas of vaporized nickel chloride is allowed to react with a reducing gas such as hydrogen. In this case, solid nickel chloride may also be heated to evaporate to produce nickel chloride gas. However, considering the oxidation of nickel chloride or preventing moisture absorption and energy efficiency, the chlorine gas is brought into contact with the metal nickel and the nickel chloride gas is continuously generated, and the nickel chloride gas is directly supplied to the reduction step, and then Connected with reducing gas In the touch, it is advantageous 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 ratio (d/D) of a number average particle diameter D to a crystallite diameter d of 0.40 or more 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，氯化鎳氣體以外之金屬氯化物氣體，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、膦氣體等及它們的混合氣體。 In the case of a method for producing an alloy powder containing nickel as a main component, examples of the metal chloride gas other than the nickel chloride gas 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, and the like, and a mixed gas thereof.

而還原性氣體可列舉出：氫氣、硫化氫氣體、氨氣、一氧化碳氣體、甲烷氣體及它們的混合氣體。特佳為氫氣、硫化氫氣體、氨氣、及它們的混合氣體。 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 gas, and a mixture thereof.

在以氣相還原反應進行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，依照在還原步驟的氯化鎳氣體之分壓與溫度等的條件，決定產生的鎳粉之粒徑。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，能調整供給至還原步驟的氯化鎳氣體的量，藉此，能控制產生的鎳粉之粒徑。 In the production process of the nickel powder 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 and aggregate, and the nickel particles are generated and grown. Then, the particle size of the produced nickel powder is determined in accordance with the conditions of the partial pressure of the nickel chloride gas in the reduction step and the temperature. 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. It can control the particle size of the produced nickel powder.

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，依照製造條件還能不使用載體氣體。因此，氣相還原反應的方面，藉由減少載體氣體的使用量及降低與此相伴的加熱能量，能謀取製造成本的削減。 In addition, since 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 can be reduced. A carrier gas is used. Therefore, in the gas phase reduction reaction, the production cost can be reduced by reducing the amount of the carrier gas used and reducing the heating energy associated therewith.

又，藉由將惰性氣體混合進於氯化步驟產生的氯化鎳氣體中，能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圧，能控制鎳粉的粒徑，能抑制粒徑的變動，並能任意設定粒徑。 Further, by mixing an 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 branching 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，起始原料之氯化鎳為讓純度99.5%以上的粒狀、塊狀、板狀等的金屬鎳，先與氯氣反應而產生氯化鎳氣體。此時的溫度係為了要充分進行反應而設為800℃以上，且為鎳的熔點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 metallic nickel such as a granular, massive or plate-like material having a purity of 99.5% or more, which is first reacted with chlorine gas to generate nickel chloride gas. The temperature at this time is 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，能以適當的氬氣、氮氣等的惰性氣體稀釋氯化鎳氣體，來控制氯化鎳氣體的分壓。藉由控制氯化鎳氣體的分壓，能控制於還原部產生的金屬粉末的粒度分布等的品質。能任意設定藉此產生的金屬粉末的品質，並能讓品質安定。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 generated in the reduction portion. The quality of the metal powder produced thereby 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, preferably less than the melting point of nickel, and 900 ° C in consideration of economy. 1100 ° C is practical.

產生如此進行還原反應之鎳粉後，將產生的鎳粉冷卻。冷卻時，為了防止因產生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，期望把藉由吹進氮氣等惰性氣體來終止還原反應的1000℃之氣流急速冷卻至400~800℃左右。然後，將產生的鎳粉例如藉由袋狀濾器等分離、回收。 After the nickel powder thus subjected to the reduction reaction is produced, 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 generated, and to obtain nickel powder having a desired particle diameter, it is desirable to terminate the reduction reaction at 1000 ° C by blowing an inert gas such as nitrogen. Rapidly cool to about 400~800 °C. Then, the produced nickel powder is separated and recovered, for example, by a bag filter or the like.

以噴霧熱分解法進行的鎳粉之製造方法中，以熱分解性的鎳化合物作為原料。具體來說係包含硝酸鹽、硫酸鹽、鹼式硝酸鹽、鹼式硫酸鹽、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。作為此時的溶媒，係使用水、乙醇、丙酮、***等。而噴霧之方法，係藉由超音波或雙噴流噴嘴等的噴霧方法進行。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，產生鎳粉。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 by the spray pyrolysis method, a thermally decomposable nickel compound is used as a raw material. Specifically, it may contain one or more of a nitrate, a sulfate, a basic nitrate, a basic sulfate, a chloride, an ammonium complex, a phosphate, a carboxylate, and an alkoxide. A solution containing the nickel compound is sprayed to form fine droplets. As the solvent at this time, water, ethanol, acetone, diethyl ether or the like is used. 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 produce 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.

以液相法進行的鎳粉之製造方法中，把含有硫酸鎳、氯化鎳或鎳錯合物之鎳水溶液，添加進氫氧化鈉等的鹼金屬氫氧化物中等，讓其接觸並產生鎳氫氧化物，接下來以肼等的還原劑將鎳氫氧化物還原得到金屬鎳粉。如此進行產生的金屬鎳粉，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 by a 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 cause contact with nickel. The hydroxide is then reduced with a reducing agent such as hydrazine to obtain a metallic nickel powder. The metal nickel powder thus produced 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，在pH與溫度經控制之特定條件下，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，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與粒子彼此的摩擦等而自表面離開所形成的微粒被除去，能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把鎳粉以純水先清洗後的水漿料中，或是將碳酸水溶液添加進把鎳粉以純水先清洗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, will 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 are sufficiently removed, and the hydroxide and the particles present on the surface of the nickel powder are separated from each other by friction or the like. The formed fine particles are removed, and a uniform nickel oxide film 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 in which nickel powder is first washed with pure water, or an aqueous solution of carbonic acid may be added to nickel powder. It is treated with water slurry which has been washed first with pure water.

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之方法 (1) A method of adding a sulfur-containing gas to the above reduction reaction

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

(3)以乾式混合鎳粉與固態的含硫化合物之方法 (3) Method for dry mixing nickel powder with solid sulfur compound

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

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

特別就能精密控制含硫量的觀點與能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，按原樣或是稀釋而使用。其中，從在常溫為氣體而容易控制流量的觀點，與混入雜質的可 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 precisely controlling the sulfur content and the viewpoint of uniformly adding 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 as it is or diluted. Among them, from the viewpoint of easily controlling the flow rate at a normal temperature as a gas, it is possible to mix impurities. From the standpoint of low energy, sulfur dioxide gas and hydrogen sulfide gas are advantageous.

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，能使用已知方法。具體來說，可列舉出：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. Specific examples include air drying in a dry state in contact with a high-temperature gas, heat drying, vacuum drying, and the like. Among them, the air flow drying is preferable because the sulfur-containing layer is not damaged by collision of particles.

接下來，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以下的一元羧酸之溶液後，加以攪拌。 Next, the obtained nickel powder is immersed in a solution containing the above-mentioned monocarboxylic acid having a hydrophilic-lipophilic balance (HLB) of 11 or less, and then stirred.

親水親油平衡值(HLB)為11以下的含一元羧酸之溶液的溶媒，能使用從純水、乙醇或工業用酒精或它們的混合物之中至少一種所選出的溶媒。特別是從鎳粉的分散容易性、經濟性的觀點來看，期望使用純水。親水親油平衡值(HLB)為11以下的一元羧酸係與上述的一元羧酸相同。 A solvent containing a solution of a monocarboxylic acid having a hydrophilic-lipophilic balance (HLB) of 11 or less can be selected from 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 desirable 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，溶解於溶媒的上述一元羧酸的量，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%。由於能充分得到鎳粉的對低極性溶媒之潤濕性及分散性之改善效果、降低乾燥後的碳濃度，所以此範圍是較佳的。 In this case, the amount of the above monocarboxylic acid dissolved in the solvent depends 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, it is preferred. It is 0.1 to 10% by mass, preferably 0.2 to 2% by mass, based on the nickel powder. This range is preferable because the effect of improving the wettability and dispersibility of the low-polarity solvent of the nickel powder and the reduction of the carbon concentration after drying can be sufficiently obtained.

又，溶媒的量，從分散的容易性、經濟性的觀點來看，較佳為把鎳粉的濃度調整成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媒中的 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 use a wet disperser to make the solvent The nickel particles are sufficiently dispersed, and stirred 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，能使用已知的方法。具體來說，可列舉出：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。另外，也可視需要加入以噴射磨機進行的粉碎處理。 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. Specific examples include air drying in a dry state in contact with a high-temperature gas, heat drying, vacuum drying, and the like. 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 may be added as needed.

然後，本發明之鎳粉能以例如添加萜品醇等的溶媒，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成粉，再以3枝輥混練之眾所皆知的方法，來容易地製造高性能的鎳糊。作為溶媒，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。而作為有機黏結劑，較佳為樹脂黏合劑，可列舉出例如：乙基纖維素、聚乙烯縮醛、丙烯酸樹脂、酸醇樹脂等。 Then, the nickel powder of the present invention can 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 a three-roller. A well-known method of mixing is to easily 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 An ester-based or propionate-based solvent such as dihydroterpineol propionate, dihydrocarvyl propionate or isodecyl propionate, or celecoxib such as celecoxib or dingsailusu. Aromatic, diethyl phthalate, etc. Further, as the organic binder, a resin binder is preferable, and examples thereof include ethyl cellulose, polyvinyl acetal, acrylic resin, and acid alcohol resin.

作為分散劑能使用眾所周知的適當藥劑，例 如能使用乙烯系聚合物、多元羧酸胺鹽、多元羧酸系等。 As the dispersing agent, a well-known appropriate agent can be used, for example. A vinyl polymer, a polyvalent carboxylic acid amine salt, a polyvalent carboxylic acid system, or the like can be used.

[實施例] [Examples]

接下來，舉出實施例與比較例來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 illustrated by the following examples and comparative examples, but this is 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個以上粒子進行圖像分析，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 500 or more 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)分析出對應於(111面)之44.5°附近的尖峰位置θ並測定半值寬B，取謝樂常數K=0.9使用謝樂的算式計算微晶直徑。 X-ray diffraction measuring device (manufactured by PANalytycal, X'pert-MPD/PRO-MPD divergence slit 0.5°, no light-receiving slit), using CuKα line (wavelength λ=1.5418Å), tube voltage 45kV, tube current 40 mA, step angle 0.02 °, scanning speed 0.04 ° / s, the diffraction angle 2θ = 43.5 ~ 45.5 ° X-ray diffraction measurements were taken. The peak position θ corresponding to the (111 plane) near 44.5° was analyzed by the attached analysis software (X'pert High Score) and the half value width B was measured. The Xiele constant K=0.9 was calculated using Xie Le's formula. diameter.

(3)雜質濃度 (3) 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分析儀(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.

(4)有機物之吸附狀態 (4) Adsorption state of organic matter

以傅立葉轉換紅外線分光光度計(Thermo Fisher Scientific Inc.製，Nicolet 6700)測定紅外線吸收光譜後，用附屬的分析軟體修正基線，分析鎳粉表面的有機物之吸附狀態。 The infrared absorption spectrum was measured by a Fourier transform infrared spectrophotometer (Nicolet 6700, manufactured by Thermo Fisher Scientific Inc.), and the baseline was analyzed with an attached analysis software to analyze the adsorption state of the organic substance on the surface of the nickel powder.

(5)碳濃度 (5) 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.

(6)去除黏結劑性 (6) Remove the binder

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，評價去除黏結劑性。熱處理造成的碳濃度脂減少率((1-熱處理前的碳濃度/熱處理後的碳濃度)×100%)若為50%以上，則評價為好(○)，若小於50%則評價為不好(×)。 About 2 g of the sample was placed on an alumina plate, and placed in a graphite tube type gas environment electric furnace (SUPERYAMA Co., Ltd., SUPER BURN SLT2035D), 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. By comparison The binder concentration was evaluated to be higher than the carbon concentration before and after the heat treatment. The carbon concentration reduction rate by the heat treatment ((1-carbon concentration before heat treatment/carbon concentration after heat treatment) × 100%) is preferably (○) if it is 50% or more, and is not evaluated if it is less than 50%. Good (×).

(7)對低極性溶媒之潤濕性 (7) Wettability to low polarity solvents

將1g的試料敷設於玻璃板上，一邊以滴管滴下二氫萜品醇乙酸酯(NIPPON TERPENE CHEMICALS Inc.製，純度95%，HLB=4.4)一邊以調色刀充分混練。此時，求取到成為糊狀為止所需要的二氫萜品醇乙酸酯之滴下量。然後，以調色刀塗開所得到的糊，觀察表面。鎳粉的對低極性溶媒之潤濕性越高，到成為糊狀為止所需要的二氫萜品醇乙酸酯的滴下量越少，所得到的糊呈現金屬光澤。在到成為糊狀為止的二氫萜品醇乙酸酯的滴下量為10滴以下且呈現金屬光澤之情形，評價為好(○)，在到成為糊狀為止的二氫萜品醇乙酸酯的滴下量超過10滴、看不出金屬光澤的情形，評價為不好(×)。 1 g of the sample was placed on a glass plate, and dihydroterpineol acetate (manufactured by NIPPON TERPENE CHEMICALS Inc., purity: 95%, HLB = 4.4) was dropped by a dropper, and kneaded thoroughly with a palette knife. At this time, the amount of dihydroterpineol acetate required to be in a paste form was determined. Then, the obtained paste was spread with a palette knife to observe the surface. The higher the wettability of the nickel powder to the low-polarity solvent, the less the amount of dihydroterpineol acetate required to form a paste, and the resulting paste exhibits metallic luster. In the case where the amount of the dihydroterpineol acetate to be in the form of a paste is 10 drops or less and the metallic luster is present, it is evaluated as good (○), and the dihydroterpineol acetic acid is formed into a paste. When the amount of the drop of the ester exceeded 10 drops and the metallic luster was not observed, it was evaluated as not good (x).

(8)在糊中的分散性 (8) Dispersion in paste

於燒杯中秤取試料0.2g，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，於雷射繞射型濕式粒度分布測定機(BECKMAN COULTER股份有限公司製，LS-230)的流動槽內裝滿二氫萜品醇乙酸酯。在試料的分散處理後，以滴管適量採取試料，導入雷射繞射型粒度分布測定機中，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，但這是為了測定粒子於二氫萜品醇乙酸酯中凝集而成之凝集體的粒度分布。粒度分布的D25、D50、D75分別意指累積體積頻率為25%、50%、75%而得的粒徑。試料在糊中的分散性越好，則凝集體的粒度變得越小。D75若為2.30μm以下，則評價為好(○)，超過2.30，則評價為不好(×)。 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, a flow tank of a laser diffraction type wet particle size distribution measuring machine (BE-MAN, manufactured by BECKMAN COULTER Co., Ltd.) was filled with dihydroterpineol acetate. After the dispersion treatment of the sample, the sample was taken in an appropriate amount in a dropper, and introduced into a laser diffraction type particle size distribution measuring machine to measure the particle size distribution. The particle size distribution thus obtained showed a grain ratio as observed by an electron microscope. The particle size distribution of the sub-particles is also a large value, but this is to determine the particle size distribution of the aggregates in which the particles are agglomerated in the dihydroterpene alcohol acetate. The particle size distributions D25, D50, and D75 mean the particle diameters obtained by accumulating the volume frequency of 25%, 50%, and 75%, respectively. The better the dispersibility of the sample in the paste, the smaller the particle size of the aggregate becomes. When D75 is 2.30 μm or less, the evaluation is good (○), and when it exceeds 2.30, it is evaluated as not good (×).

(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清洗，加以乾燥、粉碎，準備鎳粉。以電子顯微鏡對此鎳粉進行評價，結果確認是數均粒徑D為110nm、平均縱橫比為0.85、平均圓度係數為1.09之球狀鎳粉。另外，從X射線繞射測定的結果來看，微晶直徑d為54.7nm，數均粒徑與微晶直徑的比d/D為0.50。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, it is washed in pure water and an aqueous solution of carbonic acid, dried, and pulverized to prepare nickel powder. The nickel powder was evaluated by an electron microscope, and as a result, it was confirmed that the number average particle diameter D was 110 nm, the average aspect ratio was 0.85, and the average circularity coefficient was 1.09. Further, from the results of the X-ray diffraction measurement, the crystallite diameter d was 54.7 nm, and the ratio d/D of the number average particle diameter to the crystallite diameter was 0.50. The impurity concentration is such that the sodium concentration is less than 0.001% by mass and the calcium concentration is less than 0.001% by mass.

以相對於鎳粉之濃度為0.25質量%之方式，在燒瓶中秤取苯甲酸(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，以攪拌機以100rpm×30min攪拌後，加以溶解，調整成鎳粉分散液。然後，一邊讓氮氣以約100ml/min流通於燒瓶的空隙，一邊以油浴加熱燒瓶的底部至100℃，將水分加以揮發。冷卻至室溫後，回收鎳粉，以250μm的尼龍篩網過篩，當作為試樣。 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%, and pure water was added to the above nickel powder to a stirrer at 100 rpm x 30 min. After stirring, it was dissolved and adjusted to a nickel powder dispersion. Then, while allowing nitrogen gas to flow through 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.

對於所得到的試料，評價有機物之吸附狀態、碳濃度/去除黏結劑性、對低極性溶媒之潤濕性、在糊中的分散性。有機物的吸附狀態之分析結果示於第1圖，碳濃度 、去除黏結劑性、對低極性溶媒之潤濕性、在糊中的分散性之評價結果示於表2。 The obtained sample was evaluated for the adsorption state of the organic substance, the carbon concentration/debinding agent property, the wettability to the low-polarity solvent, and the dispersibility in the paste. The analysis results of the adsorption state of organic substances are shown in Fig. 1, carbon concentration The evaluation results of the removal of the binder property, the wettability to the low-polarity solvent, and the dispersibility in the paste are shown in Table 2.

(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。有機物的吸附狀態之分析結果示於第1圖，碳濃度、去除黏結劑性、對低極性溶媒之潤濕性、在糊中的分散性之評價結果示於表2。 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. The analysis results of the adsorption state of the organic substance are shown in Fig. 1, and the results of evaluation of the carbon concentration, the binder removal property, the wettability to the low-polarity solvent, and the dispersibility in the paste are shown in Table 2.

(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。有機物的吸附狀態之分析結果示於第1圖，碳濃度、去除黏結劑性、對低極性溶媒之潤濕性、在糊中的分散性之評價結果示於表2。 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. The analysis results of the adsorption state of the organic substance are shown in Fig. 1, and the results of evaluation of the carbon concentration, the binder removal property, the wettability to the low-polarity solvent, and the dispersibility in the paste are shown in Table 2.

(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。有機物的吸附狀態之分析結果示於第1圖，碳濃度、去除黏結劑性、對低極性溶媒之潤濕性、在糊中的分散性之評價結果示於表2。 In addition to the change of benzoic acid to n-decanoic acid (manufactured by Kanto Chemical Co., Ltd., deer grade 1, HLB = 5.2) 1% by mass, pure water was changed to ethanol, and the heating temperature of the oil bath was changed to 80 ° C, and Example 1 The sample was prepared in the same manner and evaluated. The analysis results of the adsorption state of the organic substance are shown in Fig. 1, and the results of evaluation of the carbon concentration, the binder removal property, the wettability to the low-polarity solvent, and the dispersibility in the paste are shown in Table 2.

(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。有機物的吸附狀態之分析結果示於第1圖，碳濃度、去除黏結劑性、對低極性溶媒之潤濕性、在糊中的分散性之評價結果示於表2。 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). The analysis results of the adsorption state of the organic substance are shown in Fig. 1, and the results of evaluation of the carbon concentration, the binder removal property, the wettability to the low-polarity solvent, and the dispersibility in the paste are shown in Table 2.

(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。有機物的吸附狀態之分析結果示於第1圖，碳濃度、去除黏結劑性、對低極性溶媒之潤濕性、在糊中的分散性之評價結果示於表2。 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). The analysis results of the adsorption state of the organic substance are shown in Fig. 1, and the results of evaluation of the carbon concentration, the binder removal property, the wettability to the low-polarity solvent, and the dispersibility in the paste are shown in Table 2.

(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。有機物的吸附狀態之分析結果示於第1圖，碳濃度、去除黏結劑性、對低極性溶媒的潤濕性、在糊中的分散性之評價結果示於表2。 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. The analysis results of the adsorption state of the organic substance are shown in Fig. 1, and the results of evaluation of the carbon concentration, the binder removal property, the wettability to the low-polarity solvent, and the dispersibility in the paste are shown in Table 2.

由紅外線吸光光譜的測定結果，添加了有機物之實施例1~4及比較例1~2，與沒有添加有機物之比較例3相比，可知紅外線吸光光譜有所變化。 As a result of measuring the infrared absorption spectrum, Examples 1 to 4 and Comparative Examples 1 and 2 in which organic substances were added showed that the infrared absorption spectrum was changed as compared with Comparative Example 3 in which no organic substance was added.

於實施例1~3，在1600cm-1附近有歸屬於羧酸陰離子的C=O反對稱伸縮之吸收峰，在1400cm-1附近有歸屬於羧酸陰離子的C=O對稱伸縮之吸收峰，以及在750、700cm-1附近有歸屬於芳香族1取代體的C=C伸縮振動之吸收峰，可知苯甲酸吸附於鎳上。 In Examples 1 to 3, there are in the vicinity of 1600cm -1 attributable to the C = O of carboxylic acid anions of the asymmetric stretching absorption peak attributable to carboxylate anion has the symmetric stretching of the C = O absorption peak near 1400cm -1, Further, in the vicinity of 750 and 700 cm -1 , there is an absorption peak of C=C stretching vibration attributed to the aromatic 1 substituent, and it is understood that benzoic acid is adsorbed on nickel.

於實施例4，在1600cm-1附近有歸屬於羧酸陰離子的C=O反對稱伸縮之吸收峰，在1400cm-1附近有歸屬於羧酸陰離子的C=O對稱伸縮之吸收峰，在2950、2850cm-1附近有歸屬於烴鏈-CH2-的伸縮振動之吸收峰，可知正癸酸吸附於鎳上。 In Example 4, there are in the vicinity of 1600cm -1 attributable to the C = O of carboxylic acid anions of the asymmetric stretching absorption peak attributable to carboxylate anion has the symmetric stretching of the C = O absorption peak near 1400cm -1, 2950 There is an absorption peak derived from the stretching vibration of the hydrocarbon chain -CH 2 - in the vicinity of 2850 cm -1 , and it is understood that n-decanoic acid is adsorbed on nickel.

於比較例1，在1600cm-1附近有歸屬於羧酸陰離子的C=O反對稱伸縮之吸收峰，以及在1400cm-1附近有歸屬於羧酸陰離子的C=O對稱伸縮之吸收峰，可知乙酸吸附於鎳上。 In Comparative Example 1, there are in the vicinity of 1600cm -1 of the absorption peak attributable to the antisymmetric stretching C = O of carboxylate anion, there is attributable to carboxylate anion, and the symmetric stretching of the C = O absorption peak near 1400cm -1, apparent Acetic acid is adsorbed on nickel.

於比較例2，在1700~1750cm-1附近有歸屬於羧酸的C=O伸縮振動，在1200cm-1附近有歸屬於羧酸的C-O伸縮振動，及在2950cm-1、2850cm-1附近有歸屬於烴鏈-CH2-的伸縮振動之吸收峰，可知有羧基的有機物吸附於鎳上。 To 2, 1700 to have assigned to the C = O stretching vibration of carboxylic acids, carboxylic acid have attributed to CO stretching vibration in the vicinity of 1200cm -1 Example Comparative near 1750cm -1, and at 2950cm -1, 2850cm -1 nearby The absorption peak of the stretching vibration attributed to the hydrocarbon chain -CH 2 - was observed to be adsorbed on the nickel by the organic substance having a carboxyl group.

就比較例3來說，沒有觀察到於實施例能看到的1400cm-1附近的歸屬於羧酸陰離子之C=O對稱伸縮之吸收峰及1600cm-1附近的歸屬於羧酸陰離子的C=O反對 稱伸縮之吸收峰。 In Comparative Example 3, it was not observed in the Examples can be seen near 1400cm -1 attributable to a carboxylate anion of the symmetric stretching of the C = O absorption peaks and the vicinity of 1600cm -1 attributable to a carboxylic acid anions of C = O opposes the absorption peak of stretching.

另外，由碳濃度的分析結果可知，實施例1~4及比較例1、3比起添加了市售的分散劑之比較例2，碳濃度更低。此外，由熱處理造成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，去除黏結劑性也更佳。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，而被認為去除黏結劑性更佳。 Further, as a result of analysis of the carbon concentration, 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, from the viewpoint of the reduction rate of the carbon concentration by the heat treatment, it is understood that Examples 1 to 4 and Comparative Example 1 are more preferable in the removal of the binder than Comparative Example 2 using a commercially available dispersant. In Examples 1 to 4 and Comparative Example 1, since the molecular weight and decomposition temperature of the added organic substance were low, it was considered that the removal of the binder property was better.

在對低極性溶媒的潤濕性之評價結果中，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，在成為糊狀為止所需要的溶媒之滴入量變少，由於所得到的糊顯示出金屬光澤，所以對低極性溶媒的潤濕性更佳。藉由以HLB低的有機物被覆鎳粉，被認為改善了潤濕性。 In the evaluation results of the wettability to the low-polarity solvent, Examples 1 to 4 in which the organic substance having a low HLB was added and Comparative Example 1 were compared with Comparative Example 1 in which acetic acid having a high HLB was added and Comparative Example 3 in which no organic substance was added. In Example 2, the amount of the solvent required for the paste to be formed was small, and since the obtained paste exhibited metallic luster, the wettability to the low-polarity solvent was further improved. It is considered that the wettability is improved by coating the nickel powder with an organic substance having a low HLB.

在糊中的分散性評價結果中，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，由於D75達2.30μm以下，所以在糊中的分散性更佳。這被認為是因為在實施例1~4及比較例2，由於對低極性溶媒的潤濕性被改善，所以在施以一定的分散力之情形變得容易分散的緣故。 In the evaluation results of the dispersibility in the paste, in Comparative Example 1 in 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. The aggregate has a small particle size, and since D75 is less than 2.30 μm, the dispersibility in the paste is better. 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一元羧酸，所以去除黏結劑性更佳。而且因為添加的有機物的HLB低，所以對低極性溶媒的潤濕性 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 removal of the binder is more preferable. And because the added organic matter has a low HLB, it is wettable to low polarity solvents. Improved, the dispersion in the paste is also improved.

就比較例1來說，由於添加的有機物為分解溫度與分子量低的一元羧酸，所以去除黏結劑性更佳。但是，因為添加的有機物的HLB高，對低極性溶媒的潤濕性不充分，其結果為在糊中的分散性也不充分。 In Comparative Example 1, since the added organic substance is a monocarboxylic acid having a decomposition temperature and a low molecular weight, the removal of the binder is more preferable. However, since the HLB of the added organic substance is high, the wettability to the low-polarity solvent is insufficient, and as a result, the dispersibility in the paste is also insufficient.

就比較例2來說，由於添加的有機物的HLB低，所以對低極性溶媒的潤濕性與在糊中的分散性被改善。但是，由於添加的有機物為分解溫度與分子量高的多元羧酸，所以去除黏結劑性差於本發明。 In Comparative Example 2, since the added organic matter had a low HLB, the wettability to the low-polarity solvent and the dispersibility in the paste were improved. However, since the added organic substance is a polycarboxylic acid having a decomposition temperature and a high molecular weight, the removal of the binder property is inferior to the present invention.

就比較例3來說，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，所以對低極性溶媒的潤濕性低，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，能提供添加的有機物之分解溫度與碳濃度為低的，有利於去除黏結劑處理，對低極性溶媒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 removing the binder treatment, improving the wettability and dispersibility of the low-polarity solvent, and being suitable for the nickel powder and nickel produced by the MLCC. paste.

Claims (5)

一種鎳粉，其為一次粒子的數均粒徑D為1μm以下之球狀鎳粉，其特徵為：鈉濃度為0.001質量%以下、鈣濃度為0.001質量%以下、碳濃度為0.05質量%以上2.0質量%以下，在以傅立葉轉換紅外線分光光度計測定時，於1600cm-1有紅外線吸光的吸收峰，在與二氫萜品醇乙酸酯混練成為糊狀時，呈現金屬光澤，於惰性環境下以300℃進行熱處理時，碳濃度的減少率為50%以上。 A nickel powder which is a spherical nickel powder having a number average particle diameter D of primary particles of 1 μm or less, and has a sodium concentration of 0.001% by mass or less, a calcium concentration of 0.001% by mass or less, and a carbon concentration of 0.05% by mass or more. 2.0% by mass or less, when measured by a Fourier transform infrared spectrophotometer, it has an absorption peak of infrared absorption at 1600 cm -1 , and when it is kneaded with dihydroterpene alcohol acetate to give a paste, it exhibits metallic luster in an inert environment. When the heat treatment is performed at 300 ° C, the carbon concentration reduction rate is 50% or more. 如請求項1之鎳粉，其表面被覆著親水親油平衡值(HLB)11以下、分解溫度300℃以下的一元羧酸。 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，其數均粒徑D與微晶直徑d的比(d/D)為0.40以上，其中，微晶直徑d係對(111)面進行X射線繞射測定，使用謝樂的算式(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 The nickel powder of claim 1 or 2 has a ratio (d/D) of the number average particle diameter D to the crystallite diameter d of 0.40 or more, wherein the crystallite diameter d is an X-ray diffraction measurement of the (111) plane. Calculated using Xie Le's formula (Formula 2), K is the Xie Le constant, λ is the X-ray wavelength, β is the half value width, and θ is the diffraction angle. 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. 一種鎳糊，其特徵為含有如請求項1至4中任一項之鎳粉。 A nickel paste characterized by containing the nickel powder of any one of claims 1 to 4.
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