TW202146133A - Carboxylic acid-containing nickel powder and method for producing carboxylic acid-containing nickel powder - Google Patents

Carboxylic acid-containing nickel powder and method for producing carboxylic acid-containing nickel powder Download PDF

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TW202146133A
TW202146133A TW110113210A TW110113210A TW202146133A TW 202146133 A TW202146133 A TW 202146133A TW 110113210 A TW110113210 A TW 110113210A TW 110113210 A TW110113210 A TW 110113210A TW 202146133 A TW202146133 A TW 202146133A
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carboxylic acid
powder
nickel powder
containing nickel
particles
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小林裕平
西村浩輔
北原万里子
岩崎峰人
釜堀康博
家田秀康
森山孝紀
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日商昭榮化學工業股份有限公司
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B1/00—Conditioning for facilitating separation by altering physical properties of the matter to be treated
    • B03B1/04—Conditioning for facilitating separation by altering physical properties of the matter to be treated by additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
    • B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
    • B07B7/00—Selective separation of solid materials carried by, or dispersed in, gas currents
    • B07B7/08—Selective separation of solid materials carried by, or dispersed in, gas currents using centrifugal force
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof

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  • Inorganic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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Abstract

The carboxylic acid-containing nickel powder of the present invention contains a plurality of nickel particles and has a carboxylic acid on a surface of each of the nickel particles, wherein by using a TG-MS, when a temperature is raised from 38ºC to 600ºC at a heating rate of 20ºC/min in an inert atmosphere, a peak is detected in a mass chromatogram of a molecular ion of the carboxylic acid and a boiling point of the carboxylic acid is Tbp [°C], a peak top of the peak exists in a range of (Tbp + 100)ºC or higher and 600ºC or lower, and a content of the carboxylic acid per 1 m2 of a surface area of the nickel particle constituting the carboxylic acid-containing nickel powder is 155 μg or more and 450 μg or less. According to the present invention, it is possible to provide the carboxylic acid-containing nickel powder having high dispersibility in a gas phase and having high dispersibility in a paste when mixed with an organic solvent or the like to form the paste.

Description

含羧酸之鎳粉末及含羧酸之鎳粉末的製造方法Carboxylic acid-containing nickel powder and method for producing carboxylic acid-containing nickel powder

本發明係有關一種含羧酸之鎳粉末及含羧酸之鎳粉末的製造方法。The present invention relates to a carboxylic acid-containing nickel powder and a method for producing the carboxylic acid-containing nickel powder.

自以往係使用導電金屬粉末作為電子元件的導電材料。在積層陶瓷電容器(Laminated Ceramic Capacitors；MCLL)中，由於陶瓷層與內部電極層的薄層化正在急速地發展中，因此具有形成薄且均勻的厚度之內部電極層的需求。為此，作為積層陶瓷電容器的內部電極用之導電金屬粉末，係具有下列的需求：粒徑分布(particle size distribution)窄，且不含有可能因包夾介電層而接觸至相鄰的內部電極之兩側進而導致電極短路的粗大粒子，並當與有機溶劑等混合來形成糊膏(paste)時，均勻地分散在糊膏中。Conventionally, conductive metal powders have been used as conductive materials for electronic components. In multilayer ceramic capacitors (MCLL), the thinning of the ceramic layer and the internal electrode layer is rapidly progressing, and thus there is a need to form an internal electrode layer with a thin and uniform thickness. Therefore, the conductive metal powder used as the internal electrode of the multilayer ceramic capacitor has the following requirements: the particle size distribution is narrow, and the conductive metal powder does not contain the possibility of contacting the adjacent internal electrode due to the sandwiched dielectric layer. On both sides, the coarse particles, which further lead to short-circuiting of electrodes, are uniformly dispersed in the paste when mixed with an organic solvent or the like to form a paste.

到目前為止，已經使用了針對以各種製造方法所製造的粉末進行分級的方法來作為用於製造所需的粒徑分布之粉末的方法。作為該分級方法，係有例如利用在氣相或液相中之粒子的沉澱速率之差異，根據粒徑的不同來對粉末進行分級的方法。在氣相中進行的分級係稱為乾式分級，而在液相中進行的分級係稱為濕式分級。雖然濕式分級具有優異的分級精度，但需要使用液體作為分散介質(disperse medium)，再者，於分級後也需要進行乾燥及粉碎。故相較於此，乾式分級之成本係非常的低。Heretofore, a method of classifying powders produced by various production methods has been used as a method for producing powders of a desired particle size distribution. As this classification method, for example, there is a method of classifying the powder according to the difference in particle size by utilizing the difference in the precipitation rate of the particles in the gas phase or the liquid phase. The classification system performed in the gas phase is called dry classification, and the classification system performed in the liquid phase is called wet classification. Although wet classification has excellent classification accuracy, it is necessary to use a liquid as a dispersion medium, and further, drying and pulverization are also required after classification. Therefore, compared to this, the cost of dry grading is very low.

然而，以往在進行該乾式分級時，由於粉末會附著在分級機的內部各處而阻塞粉末的供給口或配管內部等，因此難以長時間運轉，再者，由於分級精度低，因此具有良率低的問題。However, in the conventional dry classification, it is difficult to operate for a long time because the powder adheres to various parts of the interior of the classifier and blocks the powder supply port and the inside of the piping, etc., and it is difficult to operate for a long time. Moreover, the classification accuracy is low, so there is a good yield. low problem.

作為以解決此類問題作為目的的方法，在發明專利文獻1中，係揭示了將粉體與由乙醇(ethanol)等沸點未滿200°C之醇類所組成的助劑進行混合，一邊使助劑進行氣化一邊將粉體進行乾式分級的方法。As a method aimed at solving such problems, Patent Document 1 of the Invention discloses mixing powder with an auxiliary agent composed of alcohols having a boiling point of less than 200°C, such as ethanol, and using A method in which the powder is dry classified while the auxiliary agent is being vaporized.

又在發明專利文獻2中，係揭示了將粉體與由含有10質量%至50質量%的乙醇等醇類之醇類水溶液所組成的助劑進行混合，一邊使助劑進行氣化一邊將粉體進行乾式分級的方法。In Invention Patent Document 2, it is disclosed that powder is mixed with an auxiliary agent composed of an alcohol-based aqueous solution containing alcohols such as ethanol in an amount of 10 to 50% by mass, and the auxiliary agent is vaporized while mixing. A method for dry classification of powders.

又在發明專利文獻3中，係揭示了將由鎳(nickel；Ni)所組成的粉體與由二乙二醇(diethylene glycol)等閃點(flash point)在80°C以上之有機溶劑所組成的助劑進行混合，一邊使助劑進行氣化一邊將粉體進行乾式分級的方法。另外還揭示了將由鎳所組成的粉體與由水所組成的助劑進行混合，一邊使助劑進行氣化一邊將粉體進行乾式分級的方法。In Invention Patent Document 3, it is disclosed that a powder composed of nickel (nickel; Ni) and an organic solvent having a flash point (flash point) above 80° C. such as diethylene glycol are composed. A method of dry classification of powders while mixing the auxiliary agents, and vaporizing the auxiliary agents. Also disclosed is a method of dry classifying the powder while mixing a powder consisting of nickel and an auxiliary consisting of water, and vaporizing the auxiliary.

又在發明專利文獻4中，係揭示了將粉體與作為液體助劑的二乙二醇單甲醚(diethylene glycol monomethyl ether)進行混合來將粉體進行乾式分級的方法。〔先前技術文獻〕 〔發明專利文獻〕 Furthermore, in Invention Patent Document 4, a method of dry classifying the powder by mixing the powder with diethylene glycol monomethyl ether as a liquid auxiliary agent is disclosed. [Prior Art Documents] [Invention Patent Documents]

〔發明專利文獻1〕國際公開第2010/047175號公報。 〔發明專利文獻2〕國際公開第2010/057206號公報。 〔發明專利文獻3〕國際公開第2010/106716號公報。 〔發明專利文獻4〕國際公開第2012/124453號公報。[Invention Patent Document 1] International Publication No. 2010/047175. [Invention Patent Document 2] International Publication No. 2010/057206. [Invention Patent Document 3] International Publication No. 2010/106716. [Invention Patent Document 4] International Publication No. 2012/124453.

〔發明所欲解決之課題〕[The problem to be solved by the invention]

然而，本案發明人等在進行了研究時發現了以下問題：例如，雖然透過使乙醇等助劑吸附於粉末來進行乾式分級而變得能夠使分級機長時間運轉，但所得到的粉末中含有大量的粗大粒子，故為了減少該粗大粒子的數量而必須重複多次的分級。另外還發現了以下問題：雖然透過重複多次的分級而有使粗大粒子減少的情形，但由於花費時間及成本而使生產性(productivity)降低，並進而使獲得的粉末之良率顯著地降低。However, the inventors of the present invention discovered the following problem when conducting research. For example, although the classifier can be operated for a long time by adsorbing an auxiliary agent such as ethanol on the powder to perform dry classification, the obtained powder contains a large amount of Therefore, in order to reduce the number of the coarse particles, the classification must be repeated many times. In addition, the following problem was found: Although the number of coarse particles may be reduced by repeating the classification a plurality of times, the productivity is reduced due to the time and cost, and the yield of the obtained powder is also significantly reduced. .

再者，以上述的方式所獲得的粉末係具有難以均勻地分散在與有機溶劑等混合所獲得的糊膏中之情形。In addition, the powder obtained in the above-described manner may be difficult to uniformly disperse in the paste obtained by mixing with an organic solvent or the like.

因此，本發明的目的係在於提供在氣相中的分散性高，且當用於與有機溶劑等混合來形成糊膏時，於該糊膏中的分散性高的含羧酸之鎳粉末及其製造方法。〔解決課題之技術手段〕 Therefore, an object of the present invention is to provide a carboxylic acid-containing nickel powder having high dispersibility in the gas phase and when it is used to form a paste by mixing with an organic solvent or the like, and having high dispersibility in the paste and its manufacturing method. [Technical means for solving problems]

上述的目的係藉由以下(1)至(9)所記載的本發明而達成。 (1) 一種含羧酸之鎳粉末，係含有複數個鎳粒子，並於前述鎳粒子的表面具有羧酸之含羧酸之鎳粉末，其中： 透過TG-MS於惰性氛圍下偵測以20°C/min的升溫速度自38°C升溫至600°C時之前述羧酸的分子離子之質量層析圖(mass chromatogram)中的波峰(peak)，且將前述羧酸的沸點設定為Tbp [°C]時，前述波峰的峰頂(peak top)係存在於(Tbp +100)°C以上600°C以下的範圍內； 構成含羧酸之鎳粉末的前述鎳粒子之每1m2 表面積的前述羧酸之含量係在155 μg以上450 μg以下。The above objects are achieved by the present invention described in the following (1) to (9). (1) A carboxylic acid-containing nickel powder, which contains a plurality of nickel particles, and has a carboxylic acid-containing nickel powder with carboxylic acid on the surface of the aforementioned nickel particles, wherein: Detected by TG-MS under an inert atmosphere at 20 The peak in the mass chromatogram (mass chromatogram) of the molecular ion of the aforementioned carboxylic acid when the temperature rising rate of °C/min is increased from 38 °C to 600 °C, and the boiling point of the aforementioned carboxylic acid is set to T In bp [°C], the peak top of the aforementioned peak exists in the range of (T bp +100)°C to 600°C; per 1 m of the aforementioned nickel particles constituting the carboxylic acid-containing nickel powder 2 The content of the aforementioned carboxylic acid in the surface area is 155 μg or more and 450 μg or less.

(2) 如上述(1)所記載之含羧酸之鎳粉末，其中，透過TG-MS於惰性氛圍下以20°C/min的升溫速度自38°C升溫至600°C時，在(Tbp -50)°C以上(Tbp +50)°C以下的範圍內，係不存在前述羧酸的分子離子之質量層析圖中的波峰之峰頂。(2) The carboxylic acid-containing nickel powder according to the above (1), wherein when the temperature is raised from 38°C to 600°C at a temperature increase rate of 20°C/min through TG-MS under an inert atmosphere, in ( In the range of T bp -50) °C or higher (T bp +50) °C or lower, the peak top of the peak in the mass chromatogram of the molecular ion of the carboxylic acid does not exist.

(3) 如上述(1)或上述(2)所記載之含羧酸之鎳粉末，其中，前述羧酸的沸點係在100°C以上270°C以下。(3) The carboxylic acid-containing nickel powder according to (1) or (2) above, wherein the carboxylic acid has a boiling point of not less than 100°C and not more than 270°C.

(4) 如上述(1)至上述(3)中之任一項所記載之含羧酸之鎳粉末，其中，前述羧酸的分子量係在40以上160以下。(4) The carboxylic acid-containing nickel powder according to any one of (1) to (3) above, wherein the molecular weight of the carboxylic acid is 40 or more and 160 or less.

(5) 如上述(1)至上述(4)中之任一項所記載之含羧酸之鎳粉末，其中，前述羧酸的碳數係在2以上9以下。(5) The carboxylic acid-containing nickel powder according to any one of (1) to (4) above, wherein the carbon number of the carboxylic acid is 2 or more and 9 or less.

(6) 如上述(3)至上述(5)中之任一項所記載之含羧酸之鎳粉末，其中，前述羧酸係選自由乙酸及丙酸所組成之群中之至少一種。(6) The carboxylic acid-containing nickel powder according to any one of (3) to (5) above, wherein the carboxylic acid is at least one selected from the group consisting of acetic acid and propionic acid.

(7) 一種含羧酸之鎳粉末的製造方法，係製造上述(1)至上述(6)中之任一項所記載的含羧酸之鎳粉末的方法，其具有： 使氣體狀態的羧酸接觸分散在氣相中的鎳粉末之步驟。(7) A method for producing a carboxylic acid-containing nickel powder, the method for producing the carboxylic acid-containing nickel powder according to any one of (1) to (6) above, comprising: The step of contacting the carboxylic acid in the gaseous state with the nickel powder dispersed in the gaseous phase.

(8) 如上述(7)所記載之含羧酸之鎳粉末的製造方法，係使前述鎳粉末分散於含有氣體狀態的前述羧酸之氛圍中。(8) The method for producing a carboxylic acid-containing nickel powder according to (7) above, wherein the nickel powder is dispersed in an atmosphere containing the carboxylic acid in a gaseous state.

(9) 如上述(7)所記載之含羧酸之鎳粉末的製造方法，係生成時於氣相中呈分散狀態之前述鎳粉末在該氣相中呈分散的狀態下，於該氣相中供給氣體狀態的前述羧酸。〔發明之功效〕 (9) The method for producing a carboxylic acid-containing nickel powder according to the above (7), wherein the nickel powder in a dispersed state in a gas phase at the time of generation is dispersed in the gas phase, and in the gas phase The aforementioned carboxylic acid is supplied in a gaseous state. [Effect of invention]

根據本發明，係可提供在氣相中的分散性高，且當用於與有機溶劑等混合來形成糊膏時，於該糊膏中的分散性高的含羧酸之鎳粉末及其製造方法。According to the present invention, it is possible to provide a carboxylic acid-containing nickel powder having high dispersibility in the gas phase and mixing with an organic solvent or the like to form a paste, and its production. method.

以下係針對本發明的較佳實施態樣進行詳細說明。 [1] 含羧酸之鎳粉末 首先，針對本發明的含羧酸之鎳粉末來進行說明。The following is a detailed description of the preferred embodiments of the present invention. [1] Nickel powder containing carboxylic acid First, the carboxylic acid-containing nickel powder of the present invention will be described.

本發明的含羧酸之鎳粉末係含有複數個鎳粒子，並於前述鎳粒子的表面具有羧酸者。換言之，本發明的含羧酸之鎳粉末係含有在作為母粒子的鎳粒子之表面吸附有羧酸之吸附羧酸鎳粒子者。The carboxylic acid-containing nickel powder of the present invention contains a plurality of nickel particles and has a carboxylic acid on the surface of the nickel particles. In other words, the carboxylic acid-containing nickel powder of the present invention contains the adsorbed nickel carboxylate particles in which the carboxylic acid is adsorbed on the surface of the nickel particles serving as mother particles.

接著，本發明的含羧酸之鎳粉末係透過TG-MS(Thermogravimetry Mass Spectrometer；熱重質譜分析儀)於惰性氛圍下偵測以20°C/min的升溫速度自38°C升溫至600°C時之前述羧酸的分子離子之質量層析圖中的波峰，且將前述羧酸的沸點設定為Tbp [°C]時，前述波峰的峰頂係存在於(Tbp +100)°C以上600°C以下的範圍內，且前述鎳粒子之每1m2 表面積的前述羧酸之含量係在155 μg以上450 μg以下。Next, the carboxylic acid-containing nickel powder of the present invention is detected by TG-MS (Thermogravimetry Mass Spectrometer; thermogravimetric mass spectrometer) in an inert atmosphere from 38°C to 600°C at a heating rate of 20°C/min The peak in the mass chromatogram of the molecular ion of the aforementioned carboxylic acid at C, and when the boiling point of the aforementioned carboxylic acid is set to T bp [°C], the peak top of the aforementioned peak exists at (T bp +100)° C or more and 600°C or less, and the content of the carboxylic acid per 1 m 2 of the surface area of the nickel particles is 155 μg or more and 450 μg or less.

藉由滿足此條件，係可提供在氣相中的分散性高，且當用於與有機溶劑等混合來形成糊膏時，於該糊膏中的分散性高的含羧酸之鎳粉末。另外，藉由像這樣的含羧酸之鎳粉末在氣相中的分散性優異之特性，並透過乾式分級而可適當地去除粗大粒子，又例如透過乾式分級而可以優異的良率來順利地獲得粒徑分布狹窄(sharp)的微粉末。又藉由在含有含羧酸之鎳粉末的糊膏中含羧酸之鎳粉末的分散性優異，而可使使用了該糊膏所形成的塗膜之平滑性變得優異。By satisfying this condition, it is possible to provide a carboxylic acid-containing nickel powder that has high dispersibility in the gas phase and is used to form a paste by mixing with an organic solvent or the like. In addition, due to the excellent dispersibility of the carboxylic acid-containing nickel powder in the gas phase, coarse particles can be appropriately removed through dry classification, and, for example, through dry classification, excellent yields can be achieved. A fine powder with a sharp particle size distribution is obtained. Furthermore, since the dispersibility of the carboxylic acid-containing nickel powder in the paste containing the carboxylic acid-containing nickel powder is excellent, the smoothness of the coating film formed using the paste can be improved.

此外，透過TG-MS所偵測之羧酸的分子離子的質量層析圖中之波峰的峰頂之數值，係可例如根據羧酸在鎳粒子上的吸附形態來進行調整。更具體而言，係透過調整例如羧酸在鎳粒子上的吸附方法、吸附處理的條件、吸附量等，而可適當調整透過TG-MS所偵測之羧酸的分子離子的質量層析圖中之波峰的峰頂之數值。In addition, the value of the peak top of the peak in the mass chromatogram of the molecular ion of the carboxylic acid detected by TG-MS can be adjusted, for example, according to the adsorption form of the carboxylic acid on the nickel particles. More specifically, the mass chromatogram of the molecular ion of the carboxylic acid detected by TG-MS can be appropriately adjusted by adjusting, for example, the adsorption method of the carboxylic acid on the nickel particles, the conditions of the adsorption treatment, and the amount of adsorption. The value of the peak top of the middle wave.

又於本說明書中，粗大粒子係指相對於作為目標的粉末，例如透過如上述的分級所獲得的粉末之體積基準的累積50%粒徑(D50 )，粒徑十分大的粒子，其可設定為例如粒徑為作為目標的粉末之D50 的1.5倍以上之粒子；又可設定為例如作為目標的粉末之D50 的2.0倍以上的粒子；又可設定為例如作為目標的粉末之D50 的2.5倍以上的粒子。In the present specification, coarse particles refer to particles with a very large particle size relative to the target powder, for example, the cumulative 50% particle size (D 50 ) of the volume-based powder obtained by the above-mentioned classification. set, for example less than a target particle diameter of the powder for 1.5 times the D 50 of the particles; can, for example, set to 2.0 times or more as a target 50 of powder particles of D; D in turn set as a target, for example, powder of 2.5 times more particles than 50.

又於本說明書中，有關於體積基準的累積50%粒徑(D50 )，除非另有說明，否則係指利用雷射粒徑分布測定裝置(laser particle size distribution measuring device)所測定的粒徑分布之體積基準的積算分率50%值，其可透過利用了例如雷射繞射/散射型粒徑分布測定裝置(laser diffraction/scattering type particle size distribution measuring device)LA-960(HORIBA公司製)的測定而求得。In this specification, the cumulative 50% particle size (D 50 ) on a volume basis, unless otherwise specified, refers to the particle size measured by a laser particle size distribution measuring device The 50% value of the integrated fraction based on the volume of the distribution can be measured by, for example, a laser diffraction/scattering type particle size distribution measuring device LA-960 (manufactured by HORIBA). obtained from the measurement.

又有關於TG-MS，係可使用例如NETZSCH公司製的STA2500 Regulus作為用於將樣品進行升溫的TG-DTA(Thermogravimetry-Differential Thermal Analysis；熱重-示差同步掃描分析儀)，並使用日本電子株式會社製的JMS-Q1500GC作為用於將透過樣品的升溫而氣化的物質進行質量分析的MS(Mass Spectrometer；質譜儀)。Regarding TG-MS, for example, STA2500 Regulus manufactured by NETZSCH can be used as TG-DTA (Thermogravimetry-Differential Thermal Analysis; Thermogravimetry-Differential Thermal Analysis) for heating the sample, and JEOL Ltd. JMS-Q1500GC manufactured by the company is an MS (Mass Spectrometer; mass spectrometer) for mass analysis of a substance vaporized by the temperature rise of the sample.

另外，構成含羧酸之鎳粉末的鎳粒子之每1m2 表面積的羧酸之含量係可透過利用了CS(碳及硫)分析裝置(例如HORIBA公司製的EMIA-320V等)的測定而求得。 In addition, the content of carboxylic acid per 1 m 2 of surface area of the nickel particles constituting the carboxylic acid-containing nickel powder can be determined by measurement using a CS (carbon and sulfur) analyzer (for example, EMIA-320V manufactured by HORIBA, etc.). have to.

如上所述，本發明的含羧酸之鎳粉末係透過TG-MS的分析而在羧酸的分子離子的質量層析圖中之與羧酸的沸點不同之預定區域((Tbp +100)°C以上600°C以下的範圍)出現波峰。這被認為是由於羧酸係以特定的形態吸附於鎳粒子所致。雖然詳細的機制尚不清楚，但發明人等推測可能是例如由於羧酸係化學吸附在鎳粒子上，故相較於在物理吸附的情形況下，前者吸附地更為牢固，因而在羧酸的沸點+100°C以上的高溫區域出現波峰，進而認為在羧酸以此特定的形態吸附於鎳粒子的同時，羧酸亦以適當的比例吸附在鎳粒子的表面，藉此得以獲得如上述之優異的功效，亦即，提高在氣相中的分散性，且當用於與有機溶劑等混合來形成糊膏時，於該糊膏中的分散性提升。 As described above, the carboxylic acid-containing nickel powder of the present invention is a predetermined region ((T bp +100) different from the boiling point of the carboxylic acid in the mass chromatogram of the molecular ion of the carboxylic acid by TG-MS analysis. range from °C to 600°C) peaks appear. This is considered to be due to the adsorption of the carboxylic acid to the nickel particles in a specific form. Although the detailed mechanism is not clear, the inventors have speculated that, for example, since carboxylic acid is chemically adsorbed on nickel particles, the former is more strongly adsorbed than in the case of physical adsorption. A wave peak appears in the high temperature region above the boiling point of +100°C, and it is considered that while the carboxylic acid is adsorbed on the nickel particles in this specific form, the carboxylic acid is also adsorbed on the surface of the nickel particles in an appropriate proportion, thereby obtaining the above-mentioned Its excellent effect, that is, the dispersibility in the gas phase is improved, and when it is used to form a paste by mixing with an organic solvent or the like, the dispersibility in the paste is improved.

又藉由鎳粒子之每1m2 表面積的羧酸之含量在前述下限值以上，係可使氣相中的含羧酸之鎳粉末的分散性變得十分優異。Furthermore, when the content of the carboxylic acid per 1 m 2 of surface area of the nickel particles is at least the aforementioned lower limit value, the dispersibility of the carboxylic acid-containing nickel powder in the gas phase can be very excellent.

又藉由鎳粒子之每1m2 表面積的羧酸之含量在前述上限值以下，係可使當用於與有機溶劑等混合來形成糊膏時，於該糊膏中之含羧酸之鎳粉末的分散性變得十分優異。In addition, because the content of carboxylic acid per 1 m 2 of surface area of the nickel particles is below the aforementioned upper limit value, when it is used to form a paste by mixing with an organic solvent or the like, the carboxylic acid-containing nickel in the paste can be obtained. The dispersibility of the powder becomes very excellent.

應當說明的是，在本說明書中之「沸點」，除非另有說明，否則係指在一大氣壓下的沸點，亦即標準沸點。It should be noted that the "boiling point" in this specification, unless otherwise specified, refers to the boiling point at atmospheric pressure, that is, the standard boiling point.

再者，雖然在含羧酸之鎳粉末含有複數種羧酸的情況下，只要至少一種羧酸滿足上述的條件即可，但特別是較佳地為複數種羧酸中之含有率最高的羧酸係滿足上述的條件，更佳地為含羧酸之鎳粉末中所含有的所有種類之羧酸係滿足上述的條件。Furthermore, in the case where the carboxylic acid-containing nickel powder contains a plurality of carboxylic acids, at least one of the carboxylic acids may satisfy the above-mentioned conditions, but in particular, the carboxylic acid having the highest content rate among the plurality of carboxylic acids is preferable. The acid system satisfies the above-mentioned conditions, and it is more preferable that all kinds of carboxylic acid systems contained in the carboxylic acid-containing nickel powder satisfy the above-mentioned conditions.

如上所述，雖然在本發明的含羧酸之鎳粉末中，利用透過如上述之TG-MS的分析所偵測之羧酸的分子離子之質量層析圖中的波峰之峰頂只要存在於(Tbp +100)°C以上600°C以下的範圍內即可，但較佳地係存在於(Tbp +120)°C以上580°C以下的範圍內，更佳地係存在於(Tbp +150)°C以上560°C以下的範圍內，再更佳地係存在於(Tbp +200)°C以上540°C以下的範圍內，最佳地係存在於(Tbp +230)°C以上520°C以下的範圍內。 藉此，前述的功效係更顯著地被發揮。As described above, although in the carboxylic acid-containing nickel powder of the present invention, the peak tops of the peaks in the mass chromatogram of the molecular ions of the carboxylic acid detected by the TG-MS analysis as described above are only present in the (T bp +100) °C or more within a range of 600 °C or less, but preferably (T bp +120) °C or more and 580 °C or less, more preferably (T bp +120) °C or more. T bp +150)°C or more and 560°C or less, more preferably (T bp +200)°C or more and 540°C or less, and most preferably (T bp + 230)°C or more and 520°C or less. Thereby, the aforementioned effects are more remarkably exerted.

又雖然在本發明的含羧酸之鎳粉末中，鎳粒子之每1m2 表面積的羧酸之含量只要在155 μg以上450 μg以下即可，但較佳地在155 μg以上400 μg以下，更較佳地在155 μg以上380 μg以下，再更佳地在155 μg以上350 μg以下。其中，在本發明的含羧酸之鎳粉末中，鎳粒子之每1m2 表面積的羧酸之含量係較佳地在160 μg以上350 μg以下，更佳地在170 μg以上350 μg以下，再更佳地在250 μg以上350 μg以下。 藉此，前述的功效係更顯著地被發揮。In the carboxylic acid-containing nickel powder of the present invention, the content of carboxylic acid per 1 m 2 of surface area of the nickel particles only needs to be 155 μg or more and 450 μg or less, but preferably 155 μg or more and 400 μg or less. It is preferably 155 μg or more and 380 μg or less, and even more preferably 155 μg or more and 350 μg or less. Wherein, in the nickel powder containing carboxylic acid of the present invention, the content of carboxylic acid per 1 m 2 of surface area of the nickel particles is preferably 160 μg or more and 350 μg or less, more preferably 170 μg or more and 350 μg or less. More preferably, it is 250 μg or more and 350 μg or less. Thereby, the aforementioned effects are more remarkably exerted.

本發明的含羧酸之鎳粉末係在透過如上述的TG-MS進行分析的情況下，羧酸的分子離子之質量層析圖中的波峰之峰頂係只要存在於(Tbp +100)°C以上600°C以下的範圍內即可，又雖然羧酸的分子離子之質量層析圖中的波峰之峰頂亦可存在於上述範圍外，但較佳地係在(Tbp -50)°C以上(Tbp +50)°C以下的範圍內不存在有羧酸的分子離子之質量層析圖中的波峰之峰頂。When the carboxylic acid-containing nickel powder of the present invention is analyzed by TG-MS as described above, the peak tops of the peaks in the mass chromatogram of the molecular ions of the carboxylic acid are present as long as (T bp +100) ℃ above 600 ℃ below the scope, and although the peak top of the wave peak in the mass chromatogram of the molecular ion of the carboxylic acid can also exist outside the above-mentioned range, it is preferably within (T bp- 50 )°C or higher (T bp +50)°C or lower, the peak top of the peak in the mass chromatogram of the molecular ion having carboxylic acid does not exist.

藉此，係可使含羧酸之鎳粉末在氣相中的分散性變得更為優異。在含羧酸之鎳粉末含有複數種羧酸的情況下，較佳地為至少一種羧酸滿足上述的條件，特別是更佳地為複數種羧酸中之含有率最高的羧酸係滿足上述的條件，再更佳地為含羧酸之鎳粉末中所含有的所有種類之羧酸係滿足上述的條件。Thereby, the dispersibility in the gas phase of the carboxylic acid-containing nickel powder can be further improved. When the carboxylic acid-containing nickel powder contains a plurality of carboxylic acids, it is preferable that at least one carboxylic acid satisfies the above-mentioned conditions, and it is more preferable that the carboxylic acid having the highest content rate among the plurality of carboxylic acids satisfies the above-mentioned conditions more preferably, all kinds of carboxylic acids contained in the carboxylic acid-containing nickel powder satisfy the above-mentioned conditions.

含羧酸之鎳粉末之體積基準的累積50%粒徑D50 係較佳地為超過0.01 μm且在10 μm以下，更佳地為超過0.03 μm且在2.5μm 以下，再更佳地為超過0.05 μm且在1.2 μm以下，最佳地為超過0.10 μm且在0. 80 μm以下。Carboxylic acid-containing nickel powder on a volume basis of 50% cumulative particle diameter D 50 based preferably on more than 0.01 μm and 10 μm or less, more preferably more than 0.03 μm and at 2.5μm or less, still more preferably more than 0.05 μm and 1.2 μm or less, preferably more than 0.10 μm and 0.80 μm or less.

[1-1] 鎳粒子 鎳粒子係構成含羧酸之鎳粉末的主成分，且主要由鎳所組成者。[1-1] Nickel particles The nickel particles constitute the main component of the carboxylic acid-containing nickel powder, and are mainly composed of nickel.

鎳粒子只要是主要由鎳所組成者即可，係可由例如作為元素金屬(elemental metal)的鎳所組成者，亦可由鎳合金所組成者。 雖然鎳粒子之含有率最高的成分只要是鎳即可，但鎳粒子中之鎳以外的成分之含有率係較佳地在40質量%以下，更佳地在30質量%以下，再更佳地在20質量%以下。其中，鎳粒子中之鎳以外的成分之含有率係較佳地在10質量%以下，更佳地在5質量%以下，再更佳地在1質量%以下。特別是，鎳粒子中之鎳以外的成分係較佳地為僅含有作為不可避免的成分者，鎳粒子中之鎳以外的成分之含有率係較佳地在1000 ppm以下。As long as the nickel particles are mainly composed of nickel, for example, they may be composed of nickel which is an elemental metal, or may be composed of a nickel alloy. Although the component with the highest content of the nickel particles may be nickel, the content of components other than nickel in the nickel particles is preferably 40 mass % or less, more preferably 30 mass % or less, and still more preferably 20 mass % or less. Among them, the content of components other than nickel in the nickel particles is preferably 10 mass % or less, more preferably 5 mass % or less, and still more preferably 1 mass % or less. In particular, the components other than nickel in the nickel particles are preferably contained only as unavoidable components, and the content rate of the components other than nickel in the nickel particles is preferably 1000 ppm or less.

鎳粒子的形狀雖然未特別予以限定，但係可列舉例如球狀、片狀、粒狀等各式各樣的形狀，可自該等中選擇一種或兩種以上來組合使用。Although the shape of the nickel particle is not particularly limited, for example, various shapes such as spherical shape, flake shape, and granular shape are mentioned, and one or two or more of them can be selected and used in combination.

應當說明的是，在本說明書中，球狀係指長徑/短徑的比例在2以下的粒子之形狀。又，片狀係指長徑/短徑的比例超過2的形狀。In addition, in this specification, spherical means the shape of the particle|grains whose ratio of long axis / short axis is 2 or less. In addition, the sheet shape means a shape in which the ratio of the major axis/minor diameter exceeds 2.

作為鎳粒子的製造方法，雖然未特別予以限定，但係可列舉例如電解法、霧化(atomize)法、機械磨碎法、濕式還原法、噴霧熱分解法、化學氣相沉積法、物理氣相沉積法等。Although the method for producing nickel particles is not particularly limited, for example, electrolytic method, atomization method, mechanical grinding method, wet reduction method, spray thermal decomposition method, chemical vapor deposition method, physical Vapor deposition method, etc.

[1-2] 羧酸 含羧酸之鎳粉末係除了前述的鎳粒子之外，亦含有羧酸。[1-2] Carboxylic acid The carboxylic acid-containing nickel powder contains carboxylic acid in addition to the aforementioned nickel particles.

於含羧酸之鎳粉末中所含有的大部分的羧酸係吸附在作為母粒子的鎳粒子之表面。換言之，於含羧酸之鎳粉末中所含有的大部分的羧酸係被作為吸附羧酸鎳粒子的組成成分而含有。Most of the carboxylic acid contained in the carboxylic acid-containing nickel powder is adsorbed on the surface of the nickel particles as mother particles. In other words, most of the carboxylic acid system contained in the carboxylic acid-containing nickel powder is contained as a component for adsorbing the nickel carboxylate particles.

作為羧酸對鎳粒子的吸附形式，係可為物理吸附與化學吸附中之任一者。The adsorption form of the carboxylic acid to the nickel particles can be either physical adsorption or chemical adsorption.

作為羧酸，只要是具有羧基的化合物則不特別予以限定。The carboxylic acid is not particularly limited as long as it is a compound having a carboxyl group.

作為羧酸的沸點，較佳地在100°C以上270°C以下，更佳地在105°C以上250°C以下，再更佳地在110°C以上200°C以下，最佳地在115°C以上170°C以下。As the boiling point of the carboxylic acid, preferably above 100°C and below 270°C, more preferably above 105°C and below 250°C, more preferably above 110°C and below 200°C, most preferably at Above 115°C and below 170°C.

藉此，係可使含羧酸之鎳粉末在氣相中的分散性變得更為優異者，且當將含羧酸之鎳粉末用於與有機溶劑等混合來形成糊膏時，使含羧酸之鎳粉末於該糊膏中的分散性變得更為優異者。又在製造含羧酸之鎳粉末時，係可適當地以液體狀態處理作為原料的羧酸，而可提升操作性，並在當使羧酸在氣化的狀態下吸附於鎳粉末時，係可使羧酸以更佳的狀態吸附於鎳粉末。Thereby, the dispersibility of the carboxylic acid-containing nickel powder in the gas phase can be made more excellent, and when the carboxylic acid-containing nickel powder is mixed with an organic solvent or the like to form a paste, the The dispersibility of the nickel powder of the carboxylic acid in the paste becomes more excellent. In addition, when the carboxylic acid-containing nickel powder is produced, the carboxylic acid as a raw material can be appropriately treated in a liquid state, so that workability can be improved, and when the carboxylic acid is adsorbed to the nickel powder in a vaporized state, it is The carboxylic acid can be adsorbed on the nickel powder in a better state.

另外，羧酸係較佳地為一元羧酸(monocarboxylic acid)。 藉此，係可使含羧酸之鎳粉末在氣相中的分散性變得更為優異者，且當將含羧酸之鎳粉末用於與有機溶劑等混合來形成糊膏時，使含羧酸之鎳粉末於該糊膏中的分散性變得更為優異者。In addition, the carboxylic acid system is preferably a monocarboxylic acid. Thereby, the dispersibility of the carboxylic acid-containing nickel powder in the gas phase can be made more excellent, and when the carboxylic acid-containing nickel powder is mixed with an organic solvent or the like to form a paste, the The dispersibility of the nickel powder of the carboxylic acid in the paste becomes more excellent.

羧酸的分子量係較佳地在40以上160以下，更較佳地在50以上120以下，再更佳地在55以上100以下。The molecular weight of the carboxylic acid is preferably 40 or more and 160 or less, more preferably 50 or more and 120 or less, and still more preferably 55 or more and 100 or less.

藉此，係可使含羧酸之鎳粉末在氣相中的分散性變得更為優異者，且當將含羧酸之鎳粉末用於與有機溶劑等混合來形成糊膏時，使含羧酸之鎳粉末於該糊膏中的分散性變得更為優異者。Thereby, the dispersibility of the carboxylic acid-containing nickel powder in the gas phase can be made more excellent, and when the carboxylic acid-containing nickel powder is mixed with an organic solvent or the like to form a paste, the The dispersibility of the nickel powder of the carboxylic acid in the paste becomes more excellent.

羧酸的碳數係較佳地在2以上9以下，更佳地在2以上7以下，再更佳地在2以上5以下。The carbon number system of the carboxylic acid is preferably 2 or more and 9 or less, more preferably 2 or more and 7 or less, and still more preferably 2 or more and 5 or less.

藉此，係可使含羧酸之鎳粉末在氣相中的分散性變得更為優異者，且當將含羧酸之鎳粉末用於與有機溶劑等混合來形成糊膏時，使含羧酸之鎳粉末於該糊膏中的分散性變得更為優異者。Thereby, the dispersibility of the carboxylic acid-containing nickel powder in the gas phase can be made more excellent, and when the carboxylic acid-containing nickel powder is mixed with an organic solvent or the like to form a paste, the The dispersibility of the nickel powder of the carboxylic acid in the paste becomes more excellent.

作為羧酸雖然可列舉例如甲酸(formic acid)、乙酸(acetic acid)、丙酸(propionic acid)、異丁酸(isobutyric acid)、丁酸(butyric acid)、丁烯酸(crotonic acid)、異戊酸(isovaleric acid)、戊酸(valeric acid)、己酸(caproic acid)、庚酸(enanthic acid)、辛酸(caprylic acid)、壬酸(pelargonic acid)、乳酸(lactic acid)、乙二酸(oxalic acid)、丁二酸(succinic acid)、油酸(oleic acid)、丙烯酸(acrylic acid)、甲基丙烯酸(methacrylic acid)等，並可自該等中選擇一種或兩種以上來組合使用，但較佳地係選自由乙酸及丙酸所組成之群中之至少一種，更佳地係乙酸。Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, isobutyric acid, butyric acid, crotonic acid, isobutyric acid, and isobutyric acid. Isovaleric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lactic acid, oxalic acid (oxalic acid), succinic acid (succinic acid), oleic acid (oleic acid), acrylic acid (acrylic acid), methacrylic acid (methacrylic acid), etc., one or two or more of them can be selected and used in combination , but preferably at least one selected from the group consisting of acetic acid and propionic acid, more preferably acetic acid.

藉此，係可使含羧酸之鎳粉末在氣相中的分散性變得更為優異者，且當將含羧酸之鎳粉末用於與有機溶劑等混合來形成糊膏時，使含羧酸之鎳粉末於該糊膏中的分散性變得更為優異者。Thereby, the dispersibility of the carboxylic acid-containing nickel powder in the gas phase can be made more excellent, and when the carboxylic acid-containing nickel powder is mixed with an organic solvent or the like to form a paste, the The dispersibility of the nickel powder of the carboxylic acid in the paste becomes more excellent.

[1-3] 含羧酸之鎳粉末的用途 本發明的含羧酸之鎳粉末的用途雖然未特別予以限定，但可用作為導電粉末，特別是較佳地用作為導電膏用的導電粉末。由於粉末的分散性高，因此在糊膏中的分散性也容易變高。又特別是本發明的含羧酸之鎳粉末在被供給至如後述之分級步驟後，其中，在被供給至乾式分級步驟後，較佳地係用作為導電粉末，更較佳地係用作為導電膏用的導電粉末。又由於本發明的含羧酸之鎳粉末係流動性高，且操作性優異，因此在用於各式各樣的用途之情況下皆可容易地進行處理。[1-3] Application of Nickel Powder Containing Carboxylic Acid Although the application of the carboxylic acid-containing nickel powder of the present invention is not particularly limited, it can be used as a conductive powder, particularly preferably used as a conductive powder for a conductive paste. Since the dispersibility of the powder is high, the dispersibility in the paste is also likely to be high. In particular, the carboxylic acid-containing nickel powder of the present invention is preferably used as a conductive powder, more preferably as a conductive powder after being supplied to a classification step as described later, and after being supplied to a dry classification step. Conductive powder for conductive paste. Furthermore, since the carboxylic acid-containing nickel powder of the present invention has high fluidity and excellent handleability, it can be easily handled even when it is used in various applications.

透過使本發明的含羧酸之鎳粉末供給至如後述之乾式分級步驟，係可順利地獲得平均粒徑小，粒徑分布窄，且幾乎不含粗大粒子的微粉末。像這樣的微粉末係由於相較於分級前之本發明的含羧酸之鎳粉末具有更窄的粒徑分布，故可形成平滑性更為優異的塗膜，由此當前述微粉末被使用在內部電極時，能夠形成厚度均勻的電極層。又由於幾乎不含粗大粒子，故可適當防止導電粉末粒子接觸到內部電極兩側時所造成的短路。因此，即使是在需要如此特別高可靠性的用途上，亦可獲得令人充分滿意的功效。藉此，前述微粉末在用於形成積層陶瓷電容器或積層陶瓷電感器(Laminated ceramic inductor)、積層壓電致動器(Laminated piezoelectric actuator)等之積層陶瓷電子元件的內部導體(內部電極)或端子電極(terminal electrode)的情況下，係可更加顯著地發揮如上述的功效。By supplying the carboxylic acid-containing nickel powder of the present invention to a dry classification step as described later, a fine powder having a small average particle size, a narrow particle size distribution, and almost no coarse particles can be obtained smoothly. Such a fine powder system has a narrower particle size distribution than the carboxylic acid-containing nickel powder of the present invention before classification, so it can form a coating film with more excellent smoothness, so when the aforementioned fine powder is used. In the case of an internal electrode, an electrode layer with a uniform thickness can be formed. Furthermore, since there are almost no coarse particles, it is possible to appropriately prevent short circuits caused when the conductive powder particles come into contact with both sides of the internal electrodes. Therefore, even in applications requiring such a particularly high reliability, a sufficiently satisfactory effect can be obtained. Thereby, the aforementioned fine powder is used in the internal conductors (internal electrodes) or terminals of laminated ceramic electronic components for forming laminated ceramic capacitors, laminated ceramic inductors, laminated piezoelectric actuators, and the like. In the case of an electrode (terminal electrode), the above-mentioned effects can be more remarkably exhibited.

導電粉末亦可例如作為透過混合玻璃料(glass frit)與有機媒介物(organic vehicle)而成之導電膏用於形成電子元件的具有導電性之部位。The conductive powder can also be used, for example, as a conductive paste formed by mixing glass frit and an organic vehicle to form conductive parts of electronic components.

[2]含羧酸之鎳粉末的製造方法 接著係針對本發明的含羧酸之鎳粉末的製造方法進行說明。[2] Manufacturing method of carboxylic acid-containing nickel powder Next, the manufacturing method of the carboxylic acid-containing nickel powder of this invention is demonstrated.

本發明的含羧酸之鎳粉末的製造方法係製造前述本發明的含羧酸之鎳粉末的方法，其具有使氣體狀態的羧酸接觸分散在氣相中的複數個鎳粒子之集合體的鎳粉末之步驟。The method for producing a carboxylic acid-containing nickel powder of the present invention is a method for producing the aforementioned carboxylic acid-containing nickel powder of the present invention, which has a method of contacting a gaseous carboxylic acid with an aggregate of a plurality of nickel particles dispersed in a gas phase. Steps for nickel powder.

藉此，係可提供如前述之在氣相中的分散性高，且當用於與有機溶劑等混合來形成糊膏時，於該糊膏中的分散性高的含羧酸之鎳粉末的製造方法。另外，相較於使氣體狀態的羧酸接觸呈靜置狀態的鎳粉末之情況，由於前者之羧酸的濃度低，並可使羧酸以壓倒性的短時間吸附在鎳粒子的表面，因此在羧酸的消耗量或縮短時間的觀點上也具有益處。Thereby, it is possible to provide a carboxylic acid-containing nickel powder having high dispersibility in the gas phase as described above, and when it is used to form a paste by mixing with an organic solvent or the like, and having a high dispersibility in the paste. Production method. In addition, compared with the case where the carboxylic acid in the gas state is brought into contact with the nickel powder in the stationary state, the concentration of the carboxylic acid in the former is low, and the carboxylic acid can be adsorbed on the surface of the nickel particles in an overwhelmingly short time. There are also benefits from the viewpoint of consumption of carboxylic acid or shortening of time.

雖然本發明的含羧酸之鎳粉末的製造方法只要具有使氣體狀態的羧酸接觸分散在氣相中的鎳粉末之步驟即可，但較佳地係例如使複數個鎳粒子之集合體的鎳粉末分散於含有呈氣體狀態的羧酸之氛圍中。The method for producing a carboxylic acid-containing nickel powder of the present invention only needs to include the step of bringing the carboxylic acid in a gaseous state into contact with the nickel powder dispersed in the gas phase. Nickel powder is dispersed in an atmosphere containing carboxylic acid in gaseous state.

又在本發明的含羧酸之鎳粉末的製造方法中，亦可透過在生成時於氣相中呈分散狀態之前述鎳粉末在該氣相中呈分散的狀態下，於該氣相中供給氣體狀態的前述羧酸，來進行使氣體狀態的羧酸接觸鎳粉末的步驟。Furthermore, in the method for producing a carboxylic acid-containing nickel powder of the present invention, the nickel powder which is dispersed in the gas phase at the time of generation may be supplied in the gas phase in a state where the nickel powder is dispersed in the gas phase. The above-mentioned carboxylic acid in a gaseous state is used to carry out the step of contacting the carboxylic acid in a gaseous state with the nickel powder.

藉此，由於在氣相中生成鎳粉末後，透過在回收該鎳粉末之前送入羧酸氣體，可使羧酸氣體接觸分散狀態更佳的鎳粉末，故可使羧酸吸附地更為均勻。Thereby, after the nickel powder is formed in the gas phase, by feeding the carboxylic acid gas before recovering the nickel powder, the carboxylic acid gas can be brought into contact with the nickel powder with a better dispersion state, so that the carboxylic acid can be adsorbed more uniformly .

作為在生成時於氣相中呈分散狀態之前述鎳粉末的生成方法，係可列舉例如化學氣相沉積法、物理氣相沉積法等氣相法，或是霧化法、噴霧熱分解法等。特別是透過利用氣相法或噴霧熱分解法來生成前述鎳粉末時，係可更容易地將前述鎳粉末的粒徑調整成較佳的條件。As a method for producing the nickel powder which is dispersed in the gas phase at the time of production, for example, gas phase methods such as chemical vapor deposition and physical vapor deposition, atomization methods, spray thermal decomposition methods, and the like are exemplified. . In particular, when the nickel powder is produced by the gas phase method or the spray thermal decomposition method, the particle size of the nickel powder can be adjusted more easily to preferable conditions.

此外，在本發明的含羧酸之鎳粉末的製造方法中，只要具有使氣體狀態的羧酸接觸分散在氣相中的鎳粉末之步驟即可，並不限定於使氣體狀態的羧酸接觸剛生成的鎳粉末，亦可例如使氣體狀態的羧酸接觸回收過一次的鎳粉末。In addition, the method for producing a carboxylic acid-containing nickel powder of the present invention is not limited to bringing the carboxylic acid in a gaseous state into contact with the nickel powder dispersed in the gaseous phase as long as it has a step of bringing it into contact with the carboxylic acid in a gaseous state. The nickel powder just produced may be, for example, the nickel powder recovered once by contacting a gaseous carboxylic acid.

[3] 使用了本發明的含羧酸之鎳粉末的微粉末之製造方法 接著，針對使用了前述之本發明的含羧酸之鎳粉末的微粉末之製造方法進行說明。[3] Method for producing fine powder using carboxylic acid-containing nickel powder of the present invention Next, the manufacturing method of the fine powder using the carboxylic acid containing nickel powder of this invention mentioned above is demonstrated.

本實施態樣之微粉末的製造方法係體積基準的累積50%粒徑D50 在0.01 μm以上5.0 μm以下的範圍內之微粉末的製造方法，其具有在氣相中將D50 超過0.01 μm且在10 μm以下的含羧酸之鎳粉末進行分散，以獲得被分級之被分級粉末的被分級粉末生成步驟；以及將前述被分級粉末進行乾式分級的乾式分級步驟。The manufacturing method of the present embodiment aspect of the fine powder-based cumulative 50% particle diameter D 50 on a volume basis in the above method of manufacturing the range of 0.01 μm 5.0 [mu] m or less of fine powder having a D 50 exceeds the vapor in the 0.01 μm And the carboxylic acid-containing nickel powder of 10 μm or less is dispersed to obtain a classified powder to be classified into a classified powder generating step; and a dry classification step of dry classifying the aforementioned classified powder.

藉此，係得以提供能夠以高生產性來製造粗大粒子的個數極少，且體積基準的累積50%粒徑D50 在0.01 μm以上5.0 μm以下的範圍內之微粉末的微粉末之製造方法。Whereby, to provide a system capable of producing with high productivity extremely small number of coarse particles, and the volume-based cumulative 50% particle diameter D 50 in the above method for producing fine powder of 0.01 μm fine powder in the range of 5.0 [mu] m or less .

能夠獲得像這樣優異的功效係被認為是因為以下的因素。亦即，相較於使乙醇等助劑吸附於粉末來進行乾式分級的情況，藉由使用以預定的條件使羧酸吸附在鎳粒子的含羧酸之鎳粉末，係得以提升粉末在氣相中的分散性，並提高分級精度。藉此，能夠極度地減少所製造的微粉末中所含有的粗大粒子的個數。又藉此能夠減少分級次數，以提升生產性。It is considered that such excellent efficacy can be obtained because of the following factors. That is, compared with the case of performing dry classification by adsorbing auxiliaries such as ethanol to the powder, by using the carboxylic acid-containing nickel powder in which the carboxylic acid is adsorbed to the nickel particles under predetermined conditions, it is possible to improve the performance of the powder in the gas phase. dispersibility and improve classification accuracy. Thereby, the number of coarse particles contained in the produced fine powder can be extremely reduced. In addition, the number of classifications can be reduced to improve productivity.

再者，以上述的方式所獲得的微粉末係當用於與有機溶劑等混合來形成糊膏時，於該糊膏中的分散性會變得特別優異。因此可使使用了該糊膏所形成的塗膜之平滑性變得優異。Furthermore, when the fine powder obtained in the above-described manner is used to form a paste by mixing with an organic solvent or the like, the dispersibility in the paste is particularly excellent. Therefore, the smoothness of the coating film formed using this paste can be excellent.

另外，藉由使用本發明的含羧酸之鎳粉末，係使粉末的流動性提高，且粉末在分級機內的附著減少，而使良率提升。又藉由在分級機內的附著減少，由於分級機的粉末之供給口或配管內部等會變得不易阻塞，因此分級機的運轉時間變長，而提升了生產性。In addition, by using the carboxylic acid-containing nickel powder of the present invention, the fluidity of the powder is improved, the adhesion of the powder in the classifier is reduced, and the yield is improved. In addition, since the adhesion in the classifier is reduced, the powder supply port and the inside of the piping of the classifier are less likely to be blocked, so that the operation time of the classifier becomes longer, and the productivity is improved.

又在本實施態樣中，由於係使用預先以預定的條件使羧酸吸附於鎳粒子的含羧酸之鎳粉末，因此有利於簡化及小型化用於微粉末的製造之裝置的結構。又由於係使用預先以預定的條件使羧酸吸附於鎳粒子的含羧酸之鎳粉末，故相較於將未吸附有羧酸之鎳粉末加入分級機中的情況，前者之粉末的流動性更高，且更不易發生在分級機內的附著，使得粉末在分級機內的移動也更加順暢。Furthermore, in this embodiment, since the carboxylic acid-containing nickel powder in which the carboxylic acid is adsorbed to the nickel particles under predetermined conditions is used, it is advantageous to simplify and miniaturize the structure of the apparatus for producing the fine powder. Furthermore, since the nickel powder containing carboxylic acid is used in which the carboxylic acid is adsorbed to the nickel particles under predetermined conditions in advance, the fluidity of the former powder is higher than that of adding the nickel powder without adsorbed carboxylic acid into the classifier. Higher and less prone to adhesion in the classifier, making the powder move more smoothly in the classifier.

又在本說明書中，分級係指根據粉末的大小而將相對較大的粒子分成一組(換言之係粗粉)，將相對較小的粒子分成一組(換言之係微粉)之操作。具體而言，在本說明書中，微粉係指體積基準的累積50%粒徑D50 在0.01 μm以上5.0 μm以下的範圍內之粒子的群組，粗粉係指D50 大於微粉的粒子之群組。Also in this specification, classification refers to an operation of dividing relatively large particles into a group (in other words, coarse powder) and relatively small particles into a group (in other words, fine powder) according to the size of the powder. Specifically, in the present specification, means the volume-based powder 50% cumulative particle diameter D 50 0.01 μm or more groups of particles in the range of 5.0 [mu] m or less, the coarse powder D 50 is greater than the mean of the group of fine powder particles Group.

[3-1] 分級機 圖1係顯示為了利用本發明之含羧酸之鎳粉末來獲得粗大粒子的個數極少之微粉末所使用的分級機之一結構示例的圖式。 此外，在以下的說明中，係以圖1中的上側作為「上」，下側作為「下」來作說明。[3-1] Classifier FIG. 1 is a diagram showing an example of the structure of a classifier used to obtain a fine powder with a very small number of coarse particles using the carboxylic acid-containing nickel powder of the present invention. Note that, in the following description, the upper side in FIG. 1 is referred to as "upper" and the lower side is referred to as "lower".

分級機1係利用作用於粉末的離心力來進行分級之氣流式分級機(airflow classifier)，其具備用於形成分級室10的殼體3。The classifier 1 is an airflow classifier for classifying using centrifugal force acting on powder, and includes a casing 3 for forming a classification chamber 10 .

在分級室(分級區域)10的更上游側，係設置有用於在分級之前先將含羧酸之鎳粉末進行分散的分散區域11。分級室10係用於將被分散的含羧酸之鎳粉末進行分級的區域。On the further upstream side of the classification chamber (classification region) 10, a dispersion region 11 for dispersing the carboxylic acid-containing nickel powder prior to classification is provided. The classification chamber 10 is an area for classifying the dispersed carboxylic acid-containing nickel powder.

又，分級機1係具有：用於將含羧酸之鎳粉末導入至分散區域11內之導入口4、用於將高壓空氣(high-pressure air)(一次空氣)噴射至分散區域11內之空氣噴嘴5、用於使二次空氣流入分級室10內以在分級室10內形成渦漩氣流(swirling airflow)之導葉6、開口於分級室10的上部中央之微粉排出口7、以及沿著分級室10的下部外圍開口之粗粉排出口8。Further, the classifier 1 has an introduction port 4 for introducing the carboxylic acid-containing nickel powder into the dispersion area 11 , and an introduction port 4 for injecting high-pressure air (primary air) into the dispersion area 11 Air nozzles 5, guide vanes 6 for making secondary air flow into the classification chamber 10 to form a swirling airflow in the classification chamber 10, a fine powder discharge port 7 opened in the upper center of the classification chamber 10, and along the The coarse powder discharge port 8 which is open to the lower peripheral opening of the classifying chamber 10 is provided.

接著，針對利用此分級機1將含羧酸之鎳粉末進行分散及分級的方法進行說明。Next, a method of dispersing and classifying the carboxylic acid-containing nickel powder using the classifier 1 will be described.

含羧酸之鎳粉末係從導入口4被導入至分散區域11。藉由被噴射至分散區域11的一次空氣，含羧酸之鎳粉末係被加諸了分散力而被分散。然後，含羧酸之鎳粉末係以被分散的狀態而被導入至分級室10。The carboxylic acid-containing nickel powder is introduced into the dispersion region 11 from the introduction port 4 . By the primary air sprayed into the dispersion region 11, the carboxylic acid-containing nickel powder is imparted with a dispersing force and dispersed. Then, the carboxylic acid-containing nickel powder is introduced into the classification chamber 10 in a dispersed state.

在分級室10中，係藉由使二次空氣自導葉6流入分級室10內而使氣流在分級室10中渦旋，並自分級室10的上部中央進行排氣。藉由透過此氣流的渦漩而作用之向外的離心力與向中心移動之氣體的流動，而將固氣混合流體中的含羧酸之鎳粉末分離成粗粉及微粉。In the classification chamber 10 , the secondary air flows into the classification chamber 10 from the guide vanes 6 , so that the airflow is swirled in the classification chamber 10 , and is exhausted from the upper center of the classification chamber 10 . The carboxylic acid-containing nickel powder in the solid-gas mixed fluid is separated into coarse powder and fine powder by the centrifugal force acting outward through the vortex of the airflow and the flow of gas moving toward the center.

亦即，粗粉係透過氣流的渦漩所產生之向外的離心力在分級室10內移動至徑向外側，並從分級室10的下部外圍之粗粉排出口8被回收。另一方面，微粉係透過向中心移動之氣體的流動在分級室10內移動至徑向內側，並從分級室10的上部中央之微粉排出口7被回收。That is, the coarse powder is moved radially outward in the classifying chamber 10 by the outward centrifugal force generated by the vortex of the airflow, and is recovered from the coarse powder discharge port 8 at the lower periphery of the classifying chamber 10 . On the other hand, the fine powder moves radially inward in the classification chamber 10 by the flow of the gas moving toward the center, and is recovered from the fine powder discharge port 7 in the upper center of the classification chamber 10 .

微粉排出口7係連接有未圖示之吸式幫浦(suction pump)，微粉係與分級室10內的空氣(排氣)一同被排出及回收。The fine powder discharge port 7 is connected with a suction pump (not shown), and the fine powder is discharged and recovered together with the air (exhaust) in the classification chamber 10 .

被分級粉末生成步驟係對應於在分散區域11中執行的步驟，乾式分級步驟係對應於在分級室(分級區域)10中執行的步驟。 亦即，於分散區域11中呈被分散的狀態之含羧酸之鎳粉末，換言之，被導入分級室10的含羧酸之鎳粉末係本說明書所稱之被分級粉末。The classified powder generation step corresponds to the step performed in the dispersion area 11 , and the dry classification step corresponds to the step performed in the classification chamber (classification area) 10 . That is, the carboxylic acid-containing nickel powder in a state of being dispersed in the dispersion region 11 , in other words, the carboxylic acid-containing nickel powder introduced into the classification chamber 10 is the powder to be classified in this specification.

此外，雖然在上述的說明中係列舉了利用渦漩氣流所產生的離心力來進行分級之氣流式分級機的示例來進行了說明，但針對分級機的分級方式並未特別予以限定。亦可是例如：利用轉子(rotor)的旋轉所產生之離心力來進行分級的方式，或是利用重力來進行分級的方式，亦或是利用慣性力來進行分級的方式。Further, in the above description, an example of an air-flow classifier for classifying using centrifugal force generated by a vortex airflow has been described in series, but the classification method of the classifier is not particularly limited. For example, a method of classifying using centrifugal force generated by the rotation of a rotor, a method of classifying using gravity, or a method of classifying using inertial force may also be used.

又在本發明中，被分級粉末生成步驟及乾式分級步驟係不限定於使用同一裝置進行的情況，亦可以各自使用個別的裝置來進行。亦即，也可在利用分散機將含羧酸之鎳粉末進行分散並獲得被分級粉末之後，再利用乾式分級機將被分級粉末進行分級。Furthermore, in the present invention, the generation step of the powder to be classified and the dry classification step are not limited to the case of using the same apparatus, and may be performed using separate apparatuses. That is, after dispersing the carboxylic acid-containing nickel powder with a disperser to obtain a powder to be classified, the powder to be classified may be classified with a dry classifier.

[3-2] 被分級粉末生成步驟 在被分級粉末生成步驟中，係獲得含羧酸之鎳粉末在氣相中分散所成之被分級粉末。[3-2] Steps for generating classified powder In the generation step of the classified powder, the classified powder obtained by dispersing the carboxylic acid-containing nickel powder in the gas phase is obtained.

雖然將含羧酸之鎳粉末供給至分級機的速度，亦即例如在圖1所示之分級機1中，含羧酸之鎳粉末自導入口4向分散區域11內的供給速度也取決於分級機的大小(容量)，但較佳地在1 kg/小時以上20 kg/小時以下，更較佳地在3 kg/小時以上15 kg/小時以下，再更佳地在5 kg/小時以上12 kg/小時以下。Although the speed of supplying the carboxylic acid-containing nickel powder to the classifier, that is, for example, in the classifier 1 shown in FIG. 1, the supply speed of the carboxylic acid-containing nickel powder from the introduction port 4 into the dispersion region 11 also depends on Size (capacity) of the classifier, but preferably above 1 kg/hour and below 20 kg/hour, more preferably above 3 kg/hour and below 15 kg/hour, still more preferably above 5 kg/hour 12 kg/hour or less.

藉此，在含羧酸之鎳粉末的分散性變得更優異的同時，亦可使微粉末的生產性變得更優異。Thereby, while the dispersibility of the carboxylic acid-containing nickel powder becomes more excellent, the productivity of the fine powder can also become more excellent.

分散時之供給分散壓力，亦即例如在圖1所示的分級機1中，從空氣噴嘴5向分散區域11內所噴射的分散空氣的壓力雖然未特別予以限定，但較佳地在0.2 MPa以上1.0 MPa以下，更佳地在0.4 MPa以上0.8 MPa以下，再更佳地在0.5 MPa以上0.7 MPa以下。The supply dispersion pressure during dispersion, that is, for example, in the classifier 1 shown in FIG. 1, the pressure of the dispersion air injected from the air nozzle 5 into the dispersion area 11 is not particularly limited, but is preferably 0.2 MPa. 1.0 MPa or more, more preferably 0.4 MPa or more and 0.8 MPa or less, still more preferably 0.5 MPa or more and 0.7 MPa or less.

藉此，在含羧酸之鎳粉末的分散性變得更優異的同時，亦可使微粉末的生產性變得更優異。Thereby, while the dispersibility of the carboxylic acid-containing nickel powder becomes more excellent, the productivity of the fine powder can also become more excellent.

[3-2] 乾式分級步驟 於乾式分級步驟中，係將在被分級粉末生成步驟中所獲得的被分級粉末進行乾式分級。[3-2] Dry classification step In the dry classification step, the classified powder obtained in the classified powder generation step is dry classified.

由於被分級粉末係在氣相中適當地被分散，因此提升了乾式分級步驟的分級精度。藉此，能夠使所製造的微粉末中所含有的粗大粒子之個數變得極少。再者，藉由提升分級精度，由於可使分級次數變少，因而提升了生產性。Since the powder to be classified is appropriately dispersed in the gas phase, the classification accuracy of the dry classification step is improved. Thereby, the number of coarse particles contained in the produced fine powder can be extremely reduced. Furthermore, by improving the classification accuracy, the number of times of classification can be reduced, thereby improving productivity.

又藉由被分級粉末的流動性提高，使被分級粉末在分級機內的附著減少，因而提升了良率。又藉由在分級機內的附著減少，由於分級機的粉末之供給口或配管內部等會變得不易阻塞，因此分級機的運轉時間變長，而提升了生產性。In addition, by improving the fluidity of the powder to be classified, the adhesion of the powder to be classified in the classifier is reduced, thereby improving the yield. In addition, since the adhesion in the classifier is reduced, the powder supply port and the inside of the piping of the classifier are less likely to be blocked, so that the operation time of the classifier becomes longer, and the productivity is improved.

藉此，能夠以高生產性來製造粗大粒子的個數極少之微粉末。Thereby, a fine powder with a very small number of coarse particles can be produced with high productivity.

進行乾式分級步驟的氣相溫度雖然未特別予以限定，但較佳地在60°C以上300°C以下，更佳地在100°C以上250°C以下，再更佳地在150°C以上200°C以下。Although the gas phase temperature for carrying out the dry classification step is not particularly limited, it is preferably above 60°C and below 300°C, more preferably above 100°C and below 250°C, and more preferably above 150°C Below 200°C.

藉此，在更有效地防止因熱所導致之粒子的變形或粒子的組成材料之變質等的問題之同時，由於氣流的速度會提高而提高了離心力，又防止了水蒸氣在粒子上之附著，因此可進一步提高分級精度。另外，還可進一步提升生產性。再者，還可使微粉末中的粗大粒子之個數變得特別少。In this way, problems such as deformation of the particles due to heat and deterioration of the constituent materials of the particles are more effectively prevented, and the centrifugal force is increased due to the increase in the speed of the airflow, and the adhesion of water vapor to the particles is prevented. , so the classification accuracy can be further improved. In addition, productivity can be further improved. Furthermore, the number of coarse particles in the fine powder can be made extremely small.

進行乾式分級步驟時之抽風量，亦即例如在圖1所示的分級機1中，被連接於微粉排出口7之吸式幫浦所產生的抽風量雖然未特別予以限定，但較佳地在5.0 m3 /分鐘以上30 m3 /分鐘以下，更佳地在6.0 m3 /分鐘以上20 m3 /分鐘以下，再更佳地在7.0 m3 /分鐘以上9.0 m3 /分鐘以下。 藉此，係可更有效地進行被分級粉末的分級。The air volume when the dry classification step is performed, that is, for example, in the classifier 1 shown in FIG. 5.0 m 3 /min or more and 30 m 3 /min or less, more preferably 6.0 m 3 /min or more and 20 m 3 /min or less, still more preferably 7.0 m 3 /min or more and 9.0 m 3 /min or less. Thereby, the classification of the powder to be classified can be performed more efficiently.

進行乾式分級的抽吸壓力，亦即例如在圖1所示的分級機1中，被連接於微粉排出口7之吸式幫浦所產生的抽吸壓力雖然未特別予以限定，但較佳地在-60 kPa以上-5 kPa以下，更佳地在-50 kPa以上-10 kPa以下，再更佳地在-40 kPa以上-15 kPa以下。 藉此，係可更適切地進行被分級粉末的分級。The suction pressure for dry classification, that is, for example, in the classifier 1 shown in FIG. 1, the suction pressure generated by the suction pump connected to the fine powder discharge port 7 is not particularly limited, but preferably It is more than -60 kPa and less than 5 kPa, more preferably more than -50 kPa and less than 10 kPa, and still more preferably more than -40 kPa and less than 15 kPa. Thereby, the classification of the powder to be classified can be performed more appropriately.

藉由將被分級粉末進行乾式分級，被分級粉末係被分級成微粉與粗粉。被分級粉末係被分級成例如體積基準的累積50%粒徑D50 在0.01 μm以上5.0 μm以下的範圍內之微粉，以及D50 大於微粉之粗粉。其中，係將微粉作為上述的微粉末來回收。By dry classifying the powder to be classified, the powder to be classified is classified into fine powder and coarse powder. Graded based powder is classified into a fine powder in the range of, for example, a volume-based cumulative 50% particle diameter D 50 of more than 0.01 μm 5.0 μm or less, the fine powder and a coarse powder of greater than D 50. Among them, the fine powder is recovered as the above-mentioned fine powder.

以上述方式可製造體積基準的累積50%粒徑D50 在0.01 μm以上5.0 μm以下的範圍內之微粉末。In the above-described embodiment can be manufactured cumulative volume-based 50% particle diameter D 50 of fine powder in the range of more than 0.01 μm 5.0 μm or less of.

以此方式所製造的微粉末之粗大粒子的個數極少。又藉由在微粉末上係以較佳的狀態吸附有羧酸，故亦防止了二次凝聚。The number of coarse particles of the fine powder produced in this way is extremely small. Furthermore, since the carboxylic acid is adsorbed on the fine powder in a better state, secondary aggregation is also prevented.

更進一步地，根據上述方法，係由於分級精度提高，故可減少分級次數。另外，被分級粉末在分級機內的附著會減少。藉此提升了良率。再者，藉由在分級機內的附著減少，由於分級機的粉末之供給口或配管內部等會變得不易阻塞，因此分級機的運轉時間變長，而提升了生產性。Furthermore, according to the above-mentioned method, since the classification accuracy is improved, the number of classifications can be reduced. In addition, the adhesion of the powder to be classified in the classifier is reduced. This improves the yield. Furthermore, since the adhesion in the classifier is reduced, the powder supply port of the classifier and the inside of the piping are less likely to be clogged, so that the operation time of the classifier becomes longer, and the productivity is improved.

此外，雖然乾式分級步驟可以只進行一次，但亦可重複複數次。 藉此，係可進一步提高分級精度。Furthermore, although the dry classification step may be performed only once, it may be repeated a plurality of times. Thereby, the classification accuracy can be further improved.

乾式分級步驟中之微粉末的良率雖然未特別予以限定，但較佳地在80%以上，更佳地在81%以上，再更佳地在82%以上，最佳地在83%以上。 藉此，係使本發明的功效更為顯著。Although the yield of the fine powder in the dry classification step is not particularly limited, it is preferably above 80%, more preferably above 81%, still more preferably above 82%, and most preferably above 83%. Thereby, the effect of the present invention is made more remarkable.

此外，於本說明書中，乾式分級步驟中之微粉末的良率係根據分級前的粉末重量(亦即含羧酸之鎳粉末的重量)，以及分級後的粉末重量(亦即微粉末的重量)藉由以下公式所求得的數值： 良率(%)=(分級後的粉末重量/分級前的粉末重量)×100In addition, in this specification, the yield of the fine powder in the dry classification step is based on the weight of the powder before classification (that is, the weight of the carboxylic acid-containing nickel powder), and the weight of the powder after classification (that is, the weight of the fine powder). ) obtained by the following formula: Yield (%)=(Powder weight after classification/Powder weight before classification)×100

透過上述的本發明之方法所製造的微粉末雖然只要體積基準的累積50%粒徑D50 在0.01 μm以上5.0 μm以下的範圍內即可，但微粉末的D50 係較佳地在0.03 μm以上2.0 μm以下，更佳地在0.05 μm以上1.0 μm以下，再更佳地在0.10 μm以上0.60 μm以下。Through the above-described fine powder of the process of the present invention, although produced as long as the volume-based cumulative 50% particle size D 50 in the range of more than 0.01 μm to 5.0 [mu] m or less, the fine powder is preferably based on D 50 0.03 μm Not less than 2.0 μm, more preferably not less than 0.05 μm and not more than 1.0 μm, still more preferably not less than 0.10 μm and not more than 0.60 μm.

藉此係得以獲得具有更理想的粒徑分布之微粉末。又於習知技術中，當D50 為此範圍內的數值時，粗大粒子容易成為問題，再者粗大粒子所致使的不良影響特別容易發生。相較於此，於本發明中，即使當D50 為此範圍內的數值時，也能夠更有效地防止如上述的問題之發生。亦即，當微粉末的D50 為前述範圍內的數值時，本發明所產生的功效係更為顯著地被發揮。Thereby, a fine powder with a more ideal particle size distribution can be obtained. And in the conventional art, when the value within the range of D 50 For this reason, the problem tends to be coarse particles, resulting in the addition of coarse particles particularly prone to adverse effects. In contrast to this, in the present invention, even when D 50 is within this range, the above-mentioned problems can be prevented more effectively. That is, when D 50 of fine powder values within the aforementioned range, the effectiveness of the present invention is based is generated to play a more significant manner.

有關透過上述本發明的方法所製造的微粉末，在將利用雷射粒徑分布測定裝置所測定的粒徑分布之體積基準的積算分率10%值設定為D10 [μm]，將積算分率50%值設定為D50 [μm]，且將積算分率90%值設定為D90 [μm]時之(D90 -D10 )/D50 的值，係較佳地在0.30以上0.90以下，更佳地在0.35以上0.80以下，再更佳地在0.40以上0.75以下。Regarding the fine powder produced by the method of the present invention described above, the value of the integrated fraction of the particle size distribution measured by the laser particle size distribution measuring apparatus based on the volume of 10% is set to D 10 [μm], and the integrated fraction is set to D 10 [μm]. The value of (D 90 -D 10 )/D 50 when the 50% rate value is set to D 50 [μm], and the 90% value of the integration rate is set to D 90 [μm], is preferably 0.30 or more and 0.90 Hereinafter, it is more preferably 0.35 or more and 0.80 or less, and still more preferably 0.40 or more and 0.75 or less.

(D90 -D10 )/D50 係表示粒徑分布的均勻性之指標，當(D90 -D10 )/D50 的值越小，則粒徑分布越窄，也就表示粒徑更為均勻。(D 90 -D 10 )/D 50 is an index indicating the uniformity of particle size distribution. When the value of (D 90 -D 10 )/D 50 is smaller, the particle size distribution is narrower, which means that the particle size is smaller. to be uniform.

藉此，微粉末之粒徑變得更均勻，係適用於各種用途中。Thereby, the particle size of the fine powder becomes more uniform, and it is suitable for various applications.

又在微粉末的製造方法中，透過如以下的測定所求得之粗大粒子的個數，較佳地在30個以下，更佳地在25個以下，再更佳地在20個以下。Furthermore, in the method for producing the fine powder, the number of coarse particles determined by the following measurement is preferably 30 or less, more preferably 25 or less, and still more preferably 20 or less.

藉此，得以更有效地防止微粉末中含有粗大粒子所引起的各種問題之發生。Thereby, the occurrence of various problems caused by the inclusion of coarse particles in the fine powder can be prevented more effectively.

上述的粗大粒子之個數的測定係可例如以下述的方式來進行。 首先，將1.0 g的微粉末與20 mL的乙醇混合後，利用超音波清洗機(例如本田電子株式會社製，W-113)­進行1分鐘的處理，以製備分散液。自以此方式製備的分散液中秤取30 μL，且在鋁製樣品台上進行滴液，並使其乾燥以去除分散介質，藉此製備測定用樣品。利用掃描式電子顯微鏡(scanning electron microscope; SEM)(例如Hitachi High-Tech Corporation製，SU-1510)，並以10000倍的倍率對該測定用樣品進行50視野(visual field)的觀察。求得微粉末之具有體積基準的累積50%粒徑D50 之1.5倍以上的粒徑之粒子的總數，並將該數值作為粗大粒子的個數。The measurement of the number of the above-mentioned coarse particles can be performed, for example, in the following manner. First, 1.0 g of fine powder was mixed with 20 mL of ethanol, and then treated with an ultrasonic cleaner (for example, W-113, manufactured by Honda Electronics Co., Ltd.) for 1 minute to prepare a dispersion. From the dispersion liquid prepared in this way, 30 μL was weighed, dripped on an aluminum sample stage, and dried to remove the dispersion medium, thereby preparing a sample for measurement. This measurement sample was observed with a 50-visual field at a magnification of 10,000 times using a scanning electron microscope (SEM) (for example, SU-1510 manufactured by Hitachi High-Tech Corporation). The obtained fine powder having a volume-based cumulative total number of particles of a particle size of more than 1.5 times the 50% particle size of 50 D, and the value as the number of coarse particles.

以上雖然針對本發明的較佳實施態樣進行了說明，但本發明不限定於此。Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto.

例如，應用於微粉末之製造方法的裝置係不限定於在前述實施態樣中所說明者。［實施例］ For example, the apparatus applied to the manufacturing method of the fine powder is not limited to the one described in the foregoing embodiment. [Example]

雖然在以下列舉了具體的實施例來對本發明進行更詳細的說明，但本發明並非僅限於以下的實施例者。此外，於以下的說明中，未特別表示溫度條件、濕度條件的處理，係以室溫(25°C)、相對濕度50%所進行者。 又，針對各種測定條件，未特別表示溫度條件、濕度條件者，亦為在室溫(25°C)、相對濕度50%的數值。再者，針對含羧酸之鎳粉末、微粉末之體積基準的積算分率10%值D10 、積算分率50%值D50 、積算分率90%值D90 ，係透過利用了雷射繞射/散射型粒徑分布測定裝置LA-960(HORIBA公司製)的測定而求得。 另外，係將於以下所述的各實施例所使用的羧酸之條件統整在表1中來表示。Although the present invention will be described in more detail by way of specific examples below, the present invention is not limited to the following examples. In addition, in the following description, the processing of temperature conditions and humidity conditions is not especially shown, and it was performed at room temperature (25°C) and relative humidity of 50%. In addition, with respect to various measurement conditions, if the temperature conditions and humidity conditions are not particularly shown, they are also the values at room temperature (25°C) and relative humidity of 50%. Furthermore, the 10% integrated value D 10 , the 50% integrated value D 50 , and the 90% integrated value D 90 of the carboxylic acid-containing nickel powder and micropowder based on the volume of the powder are obtained by using a laser. It was obtained by measurement with a diffraction/scattering particle size distribution analyzer LA-960 (manufactured by HORIBA). In addition, the conditions of the carboxylic acid used in each Example to be described below are collectively shown in Table 1.

[表1]

Figure 02_image001
[Table 1]
Figure 02_image001

[4] 含羧酸之鎳粉末的製造 (實施例1) 首先，準備了體積基準的累積50%粒徑D50 為0.31 μm的鎳粉末。 將此鎳粉末在含有作為羧酸的乙酸之氛圍中進行10秒鐘的分散，藉此獲得了吸附乙酸鎳粉末之含羧酸之鎳粉末。此外，乙酸係使用了純度接近100%者(FUJIFILM Wako Pure Chemical Corporation製，特級99.7 +%)。此外，在分散鎳粉末時，含有乙酸的氛圍之溫度被調整到100°C。另外，前述氛圍中之乙酸的分壓為6.6×10-5 atm。[4] Production of carboxylic acid-containing nickel powder (Example 1) First, a nickel powder having a volume-based cumulative 50% particle size D 50 of 0.31 μm was prepared. This nickel powder was dispersed in an atmosphere containing acetic acid as a carboxylic acid for 10 seconds, whereby a carboxylic acid-containing nickel powder adsorbing the nickel acetate powder was obtained. In addition, as the acetic acid system, one having a purity of nearly 100% (manufactured by FUJIFILM Wako Pure Chemical Corporation, special grade 99.7+%) was used. In addition, when dispersing the nickel powder, the temperature of the atmosphere containing acetic acid was adjusted to 100°C. In addition, the partial pressure of acetic acid in the aforementioned atmosphere was 6.6×10 -5 atm.

(實施例2) 除了將使鎳粉末分散在含有作為羧酸之乙酸的氛圍中時之前述氛圍中的乙酸之分壓變更為6.6×10-6 atm之外，係以與前述實施例1相同的方式獲得了吸附乙酸鎳粉末的含羧酸之鎳粉末。(Example 2) The same procedure as in Example 1 described above was performed except that the partial pressure of acetic acid in the atmosphere when the nickel powder was dispersed in the atmosphere containing acetic acid as carboxylic acid was changed to 6.6×10 -6 atm The carboxylic acid-containing nickel powder that adsorbed the nickel acetate powder was obtained by the method of the method.

(實施例3) 除了使用丙酸取代乙酸來作為羧酸，並將在含有羧酸的氛圍中進行分散時的條件變更為表2所示的條件之外，係以與前述實施例1相同的方式獲得了含羧酸之鎳粉末。(Example 3) Carboxylic acid was obtained in the same manner as in Example 1, except that propionic acid was used as the carboxylic acid instead of acetic acid, and the conditions for dispersing in a carboxylic acid-containing atmosphere were changed to those shown in Table 2. Acid nickel powder.

(實施例4) 首先，準備了乙酸鎳四水合物(nickel acetate tetrahydrate；NAT)的粉末。將此乙酸鎳四水合物的粉末進行噴霧，並於氣相中加熱至1500°C，藉此獲得了在氣相中分散的鎳粉末。於該鎳粉末在氣相中分散的狀態下將氣相的溫度調整至300°C。將作為羧酸的乙酸供給至分散有該鎳粉末的氣相中，且進行10秒鐘的處理，藉此獲得了吸附乙酸鎳粉末之含羧酸之鎳粉末。乙酸係使用了純度接近100%者(FUJIFILM Wako Pure Chemical Corporation製，特級99.7 +%)。另外，係將在進行作為羧酸之乙酸的處理時之氣相中的乙酸之分壓設定為6.6×10-5 atm。此外，在供給作為羧酸之乙酸前回收鎳粉末時所測定的體積基準的累積50%粒徑D50 為0.31 μm。(Example 4) First, a powder of nickel acetate tetrahydrate (NAT) was prepared. This powder of nickel acetate tetrahydrate was sprayed and heated to 1500° C. in the gas phase, whereby nickel powder dispersed in the gas phase was obtained. The temperature of the gas phase was adjusted to 300° C. in a state where the nickel powder was dispersed in the gas phase. By supplying acetic acid as a carboxylic acid to the gas phase in which the nickel powder was dispersed, and performing a treatment for 10 seconds, a carboxylic acid-containing nickel powder adsorbing the nickel acetate powder was obtained. As the acetic acid system, one with a purity of nearly 100% (manufactured by FUJIFILM Wako Pure Chemical Corporation, special grade 99.7+%) was used. In addition, the partial pressure of acetic acid in the gas phase when the treatment of acetic acid as the carboxylic acid was performed was set to 6.6×10 −5 atm. In addition, the cumulative 50% particle diameter D 50 on a volume basis measured when the nickel powder was recovered before supplying acetic acid as the carboxylic acid was 0.31 μm.

(實施例5) 除了將供給羧酸時之氣相的溫度變更為500°C，並且將在進行作為羧酸的乙酸之處理時的氣相中之乙酸的分壓變更為1.3×10-5 atm之外，係以與前述實施例4相同的方式獲得了吸附乙酸鎳粉末之含羧酸之鎳粉末。(Example 5) Except that the temperature of the gas phase when the carboxylic acid was supplied was changed to 500°C, and the partial pressure of the acetic acid in the gas phase when the acetic acid as the carboxylic acid was treated was changed to 1.3×10 -5 Except for atm, carboxylic acid-containing nickel powder adsorbing nickel acetate powder was obtained in the same manner as in Example 4 above.

(實施例6) 除了將在進行作為羧酸的乙酸之處理時的氣相中之乙酸的分壓變更為6.6×10-5 atm之外，係以與前述實施例5相同的方式獲得了吸附乙酸鎳粉末之含羧酸之鎳粉末。(Example 6) Adsorption was obtained in the same manner as in Example 5 above, except that the partial pressure of acetic acid in the gas phase at the time of the treatment of acetic acid as carboxylic acid was changed to 6.6×10 -5 atm Carboxylic acid-containing nickel powder of nickel acetate powder.

(比較例1) 本比較例的粉末，係將於前述實施例1用作原料粉末的鎳粉末，未透過羧酸進行處理即使用。亦即，本比較例的粉末係未經羧酸處理的鎳粉末。(Comparative Example 1) The powder of this comparative example was the nickel powder used as the raw material powder in the aforementioned Example 1, and was used without being treated with carboxylic acid. That is, the powder of the present comparative example is a nickel powder not treated with carboxylic acid.

(比較例2) 首先，準備了體積基準的累積50%粒徑D50 為0.31 μm的鎳粉末。 將此鎳粉末在含有作為醇類的乙醇之氛圍中進行10秒鐘的分散，藉此獲得了作為醇類處理粉末的吸附醇類鎳粉末。此外，係將在分散鎳粉末時之含有醇類的氛圍之溫度調整至25°C。另外，係將前述氛圍中之醇類的分壓設定為9.6×10-6 atm。(Comparative Example 2) First, nickel powder having a volume-based cumulative 50% particle size D 50 of 0.31 μm was prepared. This nickel powder was dispersed in an atmosphere containing ethanol as an alcohol for 10 seconds, thereby obtaining an alcohol-treated nickel powder as an alcohol-treated powder. In addition, the temperature of the alcohol-containing atmosphere at the time of dispersing the nickel powder was adjusted to 25°C. In addition, the partial pressure of alcohols in the aforementioned atmosphere was set to 9.6×10 -6 atm.

(比較例3) 除了使用異丙醇(isopropanol)取代乙醇來作為醇類，並將在透過醇類進行處理時的氛圍中之醇類的分壓設定為8.8×10-6 atm之外，係以與前述比較例2相同的方式製造了透過有機化合物處理的處理粉末之醇類處理粉末。(Comparative Example 3) Except that isopropanol was used as the alcohol instead of ethanol, and the partial pressure of the alcohol in the atmosphere at the time of permeating the alcohol was set to 8.8×10 -6 atm, the system was In the same manner as in Comparative Example 2 described above, an alcohol-treated powder of an organic compound-treated treated powder was produced.

(比較例4) 首先，準備了體積基準的累積50%粒徑D50 為0.31 μm的鎳粉末。 將該鎳粉末靜置在含有作為羧酸的乙酸之氛圍中，藉此獲得了吸附乙酸鎳粉末的含羧酸之鎳粉末。此外，乙酸係使用了純度接近100%者(FUJIFILM Wako Pure Chemical Corporation製，特級99.7 +%)。另外，將透過乙酸所進行的處理時間設定為30分鐘，將透過乙酸進行處理時的處理溫度設定為50°C，且將透過乙酸進行處理時的氛圍中之乙酸的分壓設定為1.0×10-1 atm。(Comparative Example 4) First, a cumulative volume-based 50% particle diameter D 50 of 0.31 μm of the nickel powder. The nickel powder was allowed to stand in an atmosphere containing acetic acid as a carboxylic acid, whereby a carboxylic acid-containing nickel powder adsorbing the nickel acetate powder was obtained. In addition, as the acetic acid system, one having a purity of nearly 100% (manufactured by FUJIFILM Wako Pure Chemical Corporation, special grade 99.7+%) was used. In addition, the treatment time by permeating acetic acid was set to 30 minutes, the processing temperature when permeating acetic acid was set to 50°C, and the partial pressure of acetic acid in the atmosphere when permeating acetic acid was set to 1.0×10 -1 atm.

(比較例5及比較例6) 除了將鎳粉末在含有作為羧酸之乙酸的氛圍中進行分散時的條件變更為表2所示的條件之外，係以與前述實施例1相同的方式獲得了吸附乙酸鎳粉末的含羧酸之鎳粉末。(Comparative Example 5 and Comparative Example 6) A carboxylic acid-containing carboxylic acid adsorbing nickel acetate powder was obtained in the same manner as in Example 1, except that the conditions for dispersing the nickel powder in an atmosphere containing acetic acid as a carboxylic acid were changed to those shown in Table 2 of nickel powder.

(比較例7) 除了使用丙酸取代乙酸來作為羧酸，且將透過羧酸進行的處理時間設定為60分鐘，將透過羧酸進行處理時的處理溫度設定為120°C，以及將透過羧酸進行處理時的氛圍中之羧酸的分壓設定為5.0×10-1 atm之外，係以與前述比較例4相同的方式獲得了含羧酸之鎳粉末。(Comparative Example 7) Except that propionic acid was used as the carboxylic acid instead of acetic acid, the treatment time for permeating the carboxylic acid was set to 60 minutes, the treatment temperature when permeating the carboxylic acid was set to 120°C, and A carboxylic acid-containing nickel powder was obtained in the same manner as in Comparative Example 4 above, except that the partial pressure of the carboxylic acid in the atmosphere during the acid treatment was set to 5.0×10 −1 atm.

將前述各實施例及各比較例的粉末之製造條件，連同透過了TG-MS在惰性氛圍之氦(Helium；He)氛圍下對該等粉末所進行偵測的以20°C/min的升溫速度自38°C升溫至600°C時之羧酸的分子離子(乙酸的分子離子：m/z=60， 丙酸的分子離子：m/z=74)之質量層析圖中的波峰之峰頂的溫度，以及構成所獲得的粉末之鎳粒子的每1m2 表面積之羧酸的含量統整並表示於表2中。此外，作為MS的離子化法，係使用了EI(Electron Ionization；電子游離)法。又於表2中，亦顯示了在將於前述各實施例及比較例4至7所使用的羧酸之沸點設定為Tbp [°C]時，於(Tbp +100)°C以上600°C以下的範圍內之羧酸的分子離子之質量層析圖中有無波峰之峰頂，且亦顯示了在(Tbp -50)°C以上(Tbp +50)°C以下的範圍內之羧酸的分子離子之質量層析圖中有無波峰之峰頂。有關於TG-MS，係使用了NETZSCH公司製的STA2500 Regulus作為用於將樣品進行升溫的TG-DTA，並使用了日本電子株式會社製的JMS-Q1500GC作為用於將透過樣品的升溫而氣化的物質進行質量分析的MS。另外，構成粉末的鎳粒子之每1m2 表面積的羧酸之含量係利用CS(碳及硫)分析裝置(HORIBA公司製，EMIA-320V)來測定(1)進行使羧酸吸附的處理前之鎳粉末中的碳量，以及(2)進行使羧酸吸附的處理後之鎳粉末的碳量，並將自(2)扣除(1)所得的值作為透過使羧酸吸附的處理所增加的碳量，利用該值、碳在羧酸中的比例、以及進行使羧酸吸附的處理前之鎳粉末的比表面積而求得。另外，在表2中係將乙酸表示為「AA」、將丙酸表示為「PA」、將乙醇表示為「EtOH」、將異丙醇表示為「IPA」。The manufacturing conditions of the powders of the foregoing examples and comparative examples, together with the temperature rise at 20°C/min detected by TG-MS under an inert atmosphere of helium (Helium; He) Between the peaks in the mass chromatogram of the molecular ion of carboxylic acid (molecular ion of acetic acid: m/z=60, molecular ion of propionic acid: m/z=74) when the speed is increased from 38°C to 600°C The temperature of the peak top, and the content of the carboxylic acid per 1 m 2 of surface area of the nickel particles constituting the obtained powder are summarized and shown in Table 2. In addition, as the ionization method of MS, the EI (Electron Ionization; electron ionization) method was used. Also in Table 2, when the boiling point of the carboxylic acid used in each of the foregoing Examples and Comparative Examples 4 to 7 is set to T bp [°C], the temperature is 600°C or higher at (T bp+100)°C molecular ion mass chromatogram of acid in the range of ° C below the peak of the presence or absence of a peak, the display Qieyi ° C below the range of more than (T bp -50) ° C ( T bp +50) The mass chromatogram of the molecular ion of the carboxylic acid has or has no peak tops. Regarding TG-MS, STA2500 Regulus manufactured by NETZSCH was used as TG-DTA for heating the sample, and JMS-Q1500GC manufactured by JEOL Ltd. was used for heating and vaporizing the permeated sample. The substances were mass-analyzed by MS. In addition, the content of carboxylic acid per 1 m 2 of surface area of the nickel particles constituting the powder was measured using a CS (carbon and sulfur) analyzer (manufactured by HORIBA, EMIA-320V) (1) Before the treatment of adsorbing carboxylic acid The carbon content in the nickel powder and (2) the carbon content in the nickel powder after the carboxylic acid adsorption treatment, and the value obtained by subtracting (1) from (2) was used as the increase by the carboxylic acid adsorption treatment The carbon content was obtained by using this value, the ratio of carbon in the carboxylic acid, and the specific surface area of the nickel powder before the treatment for adsorbing the carboxylic acid. In addition, in Table 2, acetic acid is represented by "AA", propionic acid is represented by "PA", ethanol is represented by "EtOH", and isopropanol is represented by "IPA".

[表2]

Figure 02_image003
[Table 2]
Figure 02_image003

[5] 透過乾式分級之微粉末的製造 每小時分別將10 kg的前述各實施例及各比較例之粉末，亦即每小時分別將10 kg的前述各實施例及前述比較例4至7的含羧酸之鎳粉末、前述比較例1的鎳粉末、前述實施例2、3的醇類處理粉末，投入圖1所示的乾式分級機中，並將供給分散壓力設定為0.6 MPa，以獲得被分級粉末。[5] Manufacture of fine powder by dry classification 10 kg of the powders of the foregoing examples and each of the comparative examples per hour, that is, 10 kg of the carboxylic acid-containing nickel powders of the foregoing examples and the foregoing comparative examples 4 to 7, the foregoing comparative example 1, respectively, per hour. The nickel powder and the alcohol-treated powder of the aforementioned Examples 2 and 3 were put into the dry classifier shown in FIG. 1 , and the supply dispersion pressure was set to 0.6 MPa to obtain the classified powder.

接著，將被分級粉末導入分級室，並將分級機內部的溫度設定為25°C、抽風量設定為8.5 m3 /min、抽吸壓力設定為-35 kPa，以進行乾式分級而製造了微粉末。Next, the powder to be classified was introduced into the classification chamber, and the temperature inside the classifier was set to 25° C., the air volume was set to 8.5 m 3 /min, and the suction pressure was set to -35 kPa to perform dry classification to manufacture a microfabricator. powder.

其次，針對所獲得的微粉末以與上述相同的方式進一步進行了乾式分級，亦即總共進行了兩次乾式分級，並獲得了最終的微粉末。Next, the obtained fine powder was further subjected to dry classification in the same manner as described above, that is, dry classification was carried out twice in total, and the final fine powder was obtained.

[6] 評價 [6-1] 良率 針對前述各實施例及各比較例之分級前的粉末重量以及分級後的粉末重量，亦即透過進行了兩次的分級處理所獲得的微粉末之重量進行測定，並根據以下公式求得了良率。 良率(%)=(分級後的粉末重量/分級前的粉末重量)×100[6] Reviews [6-1] Yield The weight of the powder before classification and the weight of the powder after classification of the foregoing examples and comparative examples, that is, the weight of the fine powder obtained by performing the classification treatment twice, were measured, and the yield was obtained according to the following formula . Yield (%)=(Powder weight after classification/Powder weight before classification)×100

[6-2] 粒徑分布的評價 根據利用了雷射繞射/散射型粒徑分布測定裝置LA-960(HORIBA公司製)的量測，針對前述各實施例及各比較例求得原料粉末之鎳粉末以及所獲得之微粉末的粒徑分布，並由其結果分別求得了粒徑分布之體積基準的積算分率10%值(D10 )[μm]、積算分率50%值(D50 )[μm]、積算分率90%值(D90 )[μm]。[6-2] Evaluation of particle size distribution According to measurement using a laser diffraction/scattering particle size distribution measuring device LA-960 (manufactured by HORIBA), raw material powders were obtained for each of the foregoing Examples and Comparative Examples The particle size distribution of the nickel powder and the obtained fine powder was obtained, and from the results, the 10% value of the integrated fraction (D 10 ) [μm] and the 50% value of the integrated fraction (D 10 ) [μm] of the volume basis of the particle size distribution were obtained, respectively. 50 ) [μm], 90% value of integral fraction (D 90 ) [μm].

又由以上述的方式所求得之D10 [μm]、D50 [μm]、D90 [μm]的值，計算出(D90 -D10 )/D50 。 Further, (D 90 -D 10 )/D 50 was calculated from the values of D 10 [μm], D 50 [μm], and D 90 [μm] obtained as described above.

[6-3] 粗大粒子數的評價 針對前述各實施例及各比較例，將20 mL的作為分散介質之乙醇與1 g的二次分級後的粉末進行混合，利用超音波清洗機(本田電子株式會社製，W-113)­進行1分鐘的處理，以製備了分散液。自所製備的分散液中秤取30 μL，且在鋁製樣品台上進行滴液，並使其乾燥以去除分散介質，藉此製備了測定用樣品。利用掃描式電子顯微鏡(Hitachi High-Tech Corporation製，SU-1510)，並將前述樣品擴大至10000倍來進行了50視野的觀察。利用上述[6-2]的方式所求得之粒徑，以對象物之微粉末的D50 之2.0倍以上的粒子作為粗大粒子，並求得了粗大粒子數。[6-3] Evaluation of the number of coarse particles For each of the foregoing Examples and Comparative Examples, 20 mL of ethanol as a dispersion medium was mixed with 1 g of the powder after secondary classification, and an ultrasonic cleaner (Honda Electronics Co., Ltd.) was used to mix Co., Ltd., W-113) was treated for 1 minute to prepare a dispersion. From the prepared dispersion liquid, 30 μL was weighed, dripped on an aluminum sample stage, and dried to remove the dispersion medium, thereby preparing a sample for measurement. Using a scanning electron microscope (SU-1510, manufactured by Hitachi High-Tech Corporation), the above-mentioned sample was enlarged to 10,000 times, and observation of 50 fields of view was performed. The determined using the [6-2] above-described manner particle size, as particles of the fine powder of the object D 50 of 2.0 times as coarse particles, and the obtained coarse particles.

[6-4] 塗膜的平滑性 將於上述[4]所獲得之前述各實施例及各比較例的粉末，亦即100重量份之實施分級處理前的粉末、3.0重量份之乙基纖維素(ethyl cellulose)樹脂(陶氏化學公司製，STD100)、100重量份之乙酸二氫萜品醇(dihydroterpineol acetate)進行混合，並透過混合式攪拌器(hybrid mixer)(THINKY公司製，ARE-310)在2000 rpm下混合2分鐘，以獲得鎳膏(nickel paste)。將所獲得的鎳膏以10 μm的膜厚進行鑄造(casting)，並使用微細形狀測定器(fine shape measuring instrument)(小坂研究所製，ET3000i)測定了表面粗糙度(surface roughness)Ra。[6-4] Smoothness of coating film The powders of the foregoing examples and comparative examples obtained in the above [4], that is, 100 parts by weight of the powder before the classification treatment, and 3.0 parts by weight of an ethyl cellulose resin (Dow Chemical) Company made, STD100), 100 parts by weight of dihydroterpineol acetate (dihydroterpineol acetate) were mixed, and mixed with a hybrid mixer (made by THINKY, ARE-310) at 2000 rpm for 2 minutes, to obtain a nickel paste. The obtained nickel paste was cast with a film thickness of 10 μm, and the surface roughness Ra was measured using a fine shape measuring instrument (manufactured by Kosaka Laboratory, ET3000i).

又針對上述[5]所獲得之前述各實施例及各比較例的微粉末，係以與上述相同的方式進行了糊膏的製備，以及使用了該糊膏之塗膜的形成及表面粗糙度的測定。For the fine powders of the aforementioned examples and comparative examples obtained in the above [5], the preparation of the paste was carried out in the same manner as above, and the formation and surface roughness of the coating film using the paste were carried out. measurement.

將該等結果統整並示於表3中。另外，針對前述各實施例所獲得的微粉末，以上述[6-3]所示的方法求取各微粉末的具有體積基準之累積50%粒徑D50 為3.0倍以上之粒徑的粒子個數時，係在任一實施例中皆未含有此類粒子。These results are combined and presented in Table 3. In addition, with respect to the fine powder obtained in each of the foregoing examples, particles having a particle size of 3.0 times or more the cumulative 50% particle size D 50 on a volume basis of each fine powder was obtained by the method shown in the above [6-3] In the case of the number of particles, such particles are not contained in any of the examples.

[表3]

Figure 02_image005
[table 3]
Figure 02_image005

由表3可明顯看到，在前述各實施例中係能夠以高良率來順利地製造出D50 在0.01 μm以上5.0 μm以下的範圍內，且粗大粒子的個數極少之微粉末。藉此，前述各實施例的含羧酸之鎳粉末可以說是在氣相中的分散性優異。又於前述各實施例中，使用糊膏所形成的塗膜係表面粗糙度小且平滑性高。藉此，前述各實施例的含羧酸之鎳粉末可以說是在糊膏中的分散性優異。〔產業上的可利用性〕 It can be clearly seen from Table 3 that in the foregoing examples, fine powders with a D 50 in the range of 0.01 μm to 5.0 μm and a very small number of coarse particles can be successfully produced with high yield. Therefore, the carboxylic acid-containing nickel powder of each of the foregoing examples can be said to be excellent in dispersibility in the gas phase. Also in the foregoing embodiments, the coating film formed by using the paste has small surface roughness and high smoothness. Therefore, it can be said that the carboxylic acid-containing nickel powder of each of the foregoing examples has excellent dispersibility in the paste. [Industrial Availability]

本發明之含羧酸之鎳粉末係含有複數個鎳粒子，並於前述鎳粒子的表面具有羧酸者，其透過TG-MS於惰性氛圍下偵測以20°C/min的升溫速度自38°C升溫至600°C時之前述羧酸的分子離子之質量層析圖中的波峰，且將前述羧酸的沸點設定為Tbp [°C]時，前述波峰的峰頂係存在於(Tbp +100)°C以上600°C以下的範圍內，且構成含羧酸之鎳粉末的前述鎳粒子之每1m2 表面積的前述羧酸之含量係在155 μg以上450 μg以下。藉此而得以提供在氣相中的分散性高，且當用於與有機溶劑等混合來形成糊膏時，於該糊膏中的分散性高的含羧酸之鎳粉末。又，本發明之含羧酸之鎳粉末的製造方法係製造本發明之含羧酸之鎳粉末的方法，其具有使氣體狀態的羧酸接觸分散在氣相中的鎳粉末之步驟。藉此而得以提供在氣相中的分散性高，且當用於與有機溶劑等混合來形成糊膏時，於該糊膏中的分散性高的含羧酸之鎳粉末的製造方法。因此，本發明的含羧酸之鎳粉末及含羧酸之鎳粉末的製造方法係具有產業上的可利用性。The carboxylic acid-containing nickel powder of the present invention contains a plurality of nickel particles and has carboxylic acid on the surface of the nickel particles, which is detected by TG-MS in an inert atmosphere at a heating rate of 20°C/min from 38°C The peak in the mass chromatogram of the molecular ion of the aforementioned carboxylic acid when the temperature is raised to 600 °C, and when the boiling point of the aforementioned carboxylic acid is set to T bp [°C], the peak top of the aforementioned peak exists in ( T bp + 100°C or more and 600°C or less, and the content of the carboxylic acid per 1 m 2 surface area of the nickel particles constituting the carboxylic acid-containing nickel powder is 155 μg or more and 450 μg or less. Thereby, it is possible to provide a carboxylic acid-containing nickel powder having high dispersibility in the gas phase and when it is used to form a paste by mixing with an organic solvent or the like, and having high dispersibility in the paste. Moreover, the manufacturing method of the carboxylic acid-containing nickel powder of this invention is a method of manufacturing the carboxylic acid-containing nickel powder of this invention, and has the process of making the carboxylic acid in gaseous state contact with the nickel powder dispersed in the gas phase. Thereby, it is possible to provide a method for producing a carboxylic acid-containing nickel powder having high dispersibility in the gas phase and mixing with an organic solvent or the like to form a paste, which has high dispersibility in the paste. Therefore, the manufacturing method of the carboxylic acid-containing nickel powder and the carboxylic acid-containing nickel powder of the present invention has industrial applicability.

1:分級機 3:殼體 4:導入口 5:空氣噴嘴 6:導葉 7:微粉排出口 8:粗粉排出口 10:分級室(分級區域) 11:分散區域1: Classifier 3: Shell 4: Import port 5: Air nozzle 6: Guide vanes 7: Micro powder discharge port 8: Coarse powder discharge port 10: Grading room (grading area) 11: Scattered Area

〔圖1〕圖1係顯示為了利用本發明之含羧酸之鎳粉末來獲得粗大粒子的個數極少之微粉末所使用的分級機之一結構示例的圖式。[Fig. 1] Fig. 1 is a diagram showing an example of the structure of a classifier used to obtain a fine powder with a very small number of coarse particles using the carboxylic acid-containing nickel powder of the present invention.

1:分級機 1: Classifier

3:殼體 3: Shell

4:導入口 4: Import port

5:空氣噴嘴 5: Air nozzle

6:導葉 6: Guide vanes

7:微粉排出口 7: Micro powder discharge port

8:粗粉排出口 8: Coarse powder discharge port

10:分級室(分級區域) 10: Grading room (grading area)

11:分散區域 11: Scattered Area

Claims (9)

一種含羧酸之鎳粉末，係含有複數個鎳粒子，並於前述鎳粒子的表面具有羧酸之含羧酸之鎳粉末，其中： 透過TG-MS於惰性氛圍下偵測以20°C/min的升溫速度自38°C升溫至600°C時之前述羧酸的分子離子之質量層析圖中的波峰，且將前述羧酸的沸點設定為Tbp [°C]時，前述波峰的峰頂係存在於(Tbp +100)°C以上600°C以下的範圍內； 構成含羧酸之鎳粉末的前述鎳粒子之每1m2 表面積的前述羧酸之含量係在155 μg以上450 μg以下。A carboxylic acid-containing nickel powder, which contains a plurality of nickel particles, and has a carboxylic acid-containing nickel powder with carboxylic acid on the surface of the aforementioned nickel particles, wherein: Detected by TG-MS under an inert atmosphere at 20°C/ The peak in the mass chromatogram of the molecular ion of the aforementioned carboxylic acid when the heating rate of min is raised from 38°C to 600°C, and the boiling point of the aforementioned carboxylic acid is set to T bp [°C], the peak of the aforementioned peak is The peak top is present in the range of (T bp +100) ° C or more and 600 ° C or less; The content of the aforementioned carboxylic acid per 1 m 2 surface area of the aforementioned nickel particles constituting the carboxylic acid-containing nickel powder is at least 155 μg 450 μg or less. 如請求項1所記載之含羧酸之鎳粉末，其中，透過TG-MS於惰性氛圍下以20°C/min的升溫速度自38°C升溫至600°C時，在(Tbp -50)°C以上(Tbp +50)°C以下的範圍內，係不存在前述羧酸的分子離子之質量層析圖中的波峰之峰頂。The carboxylic acid-containing nickel powder according to claim 1, wherein when the temperature is raised from 38°C to 600°C at a heating rate of 20°C/min through TG-MS under an inert atmosphere, at ( Tbp- 50°C) ) °C or higher (T bp +50) °C or lower, the peak top of the peak in the mass chromatogram of the molecular ion of the carboxylic acid does not exist. 如請求項1或請求項2所記載之含羧酸之鎳粉末，其中，前述羧酸的沸點係在100°C以上270°C以下。The carboxylic acid-containing nickel powder according to claim 1 or claim 2, wherein the boiling point of the carboxylic acid is 100°C or higher and 270°C or lower. 如請求項1或請求項2所記載之含羧酸之鎳粉末，其中，前述羧酸的分子量係在40以上160以下。The carboxylic acid-containing nickel powder according to claim 1 or claim 2, wherein the molecular weight of the carboxylic acid is 40 or more and 160 or less. 如請求項1或請求項2所記載之含羧酸之鎳粉末，其中，前述羧酸的碳數係在2以上9以下。The carboxylic acid-containing nickel powder according to claim 1 or claim 2, wherein the carbon number of the carboxylic acid is 2 or more and 9 or less. 如請求項3所記載之含羧酸之鎳粉末，其中，前述羧酸係選自由乙酸及丙酸所組成之群中之至少一種。The carboxylic acid-containing nickel powder according to claim 3, wherein the carboxylic acid is at least one selected from the group consisting of acetic acid and propionic acid. 一種含羧酸之鎳粉末的製造方法，係製造請求項1至請求項6中之任一項所記載的含羧酸之鎳粉末的方法，其具有： 使氣體狀態的羧酸接觸分散在氣相中的鎳粉末之步驟。A method for producing a carboxylic acid-containing nickel powder, the method for producing the carboxylic acid-containing nickel powder described in any one of claim 1 to claim 6, comprising: The step of contacting the carboxylic acid in the gaseous state with the nickel powder dispersed in the gaseous phase. 如請求項7所記載之含羧酸之鎳粉末的製造方法，係使前述鎳粉末分散於含有氣體狀態的前述羧酸之氛圍中。The method for producing a carboxylic acid-containing nickel powder according to claim 7, wherein the nickel powder is dispersed in an atmosphere containing the carboxylic acid in a gaseous state. 如請求項7所記載之含羧酸之鎳粉末的製造方法，係生成時於氣相中呈分散狀態之前述鎳粉末在該氣相中呈分散的狀態下，於該氣相中供給氣體狀態的前述羧酸。The method for producing a carboxylic acid-containing nickel powder according to claim 7, wherein the nickel powder in a dispersed state in a gas phase at the time of generation is supplied in a gaseous state in the gas phase in a state where the nickel powder is dispersed in the gas phase of the aforementioned carboxylic acids.
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