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WO2008001741A1 - Fines particules de nickel, procédé de fabrication de celles-ci, et composition fluide les utilisant - Google Patents

Fines particules de nickel, procédé de fabrication de celles-ci, et composition fluide les utilisant Download PDF

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Publication number
WO2008001741A1
WO2008001741A1 PCT/JP2007/062741 JP2007062741W WO2008001741A1 WO 2008001741 A1 WO2008001741 A1 WO 2008001741A1 JP 2007062741 W JP2007062741 W JP 2007062741W WO 2008001741 A1 WO2008001741 A1 WO 2008001741A1
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Prior art keywords
fine particles
nickel
nickel fine
compound
reducing agent
Prior art date
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Ceased
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PCT/JP2007/062741
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English (en)
Japanese (ja)
Inventor
Masanori Tomonari
Kiyonobu Ida
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Ishihara Sangyo Kaisha Ltd
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Ishihara Sangyo Kaisha Ltd
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Priority to JP2008522579A priority Critical patent/JP5294851B2/ja
Publication of WO2008001741A1 publication Critical patent/WO2008001741A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the present invention relates to nickel fine particles, a method for producing the same, and a flowable composition using the same, and particularly nickel fine particles suitably used for producing an electrode of a multilayer ceramic capacitor, a circuit of a printed wiring board, and the like. And a method for producing the same and a fluid composition using the same.
  • Metallic nickel fine particles are an inexpensive material having good electrical conductivity, and are excellent in oxidation resistance and corrosion resistance. For this reason, it is widely used as a material for ensuring electrical continuity, such as circuit forming members for printed wiring boards, various electrical contact members, external electrode members such as capacitors, etc. It is also beginning to be used for electrodes.
  • Multilayer ceramic capacitors are rapidly spreading compared to other types of capacitors, such as electrolytic capacitors and film capacitors, because they are easy to obtain large capacities, are easy to mount, and have high safety and stability. With the recent miniaturization of electronic devices, multilayer ceramic capacitors are also in the direction of miniaturization. However, to maintain a large capacity, it is necessary to reduce the size without reducing the number of ceramic sheets stacked, such as strength. In this respect, there is a limit to the thinning of the sheet, so the internal ceramic electrode is made thin by using fine metallic nickel particles to realize a miniaturization of the multilayer ceramic capacitor.
  • nickel fine particles are usually dispersed in a solvent or mixed with a binder such as an epoxy resin to form a paste, paint or ink.
  • a fluid composition such as paste “paint” ink.
  • the flowable composition is coated with a pattern of a circuit or an electrode on the substrate by a method such as screen printing or ink jet printing, and then heated to form a metallic nickel particulate. Are fused to form a fine electrode.
  • the fluid composition is applied onto a thin ceramic sheet, the sheets are laminated, and then heated and fired to form the internal electrode. Forming.
  • a hydrazine-based reducing agent is added and mixed in a liquid medium containing a nickel compound such as nickel carbonate, nickel chloride, nickel acetate, etc., and the temperature is 100 ° C or lower.
  • a method of heating by heating see Patent Document 1.
  • a noble metal compound such as palladium chloride is added as a reaction initiator to a mixed aqueous solution of nickel, a reducing agent, and a complexing agent to cause a reduction reaction, and then nickel ions, a reducing agent, and pH are adjusted.
  • a method of adding an agent is also known.
  • Patent Document 1 JP-A-53-95165
  • Patent Document 2 Japanese Patent Laid-Open No. 63-274706
  • Patent Documents 1 and 2 Although the techniques described in Patent Documents 1 and 2 produce fine metallic nickel fine particles, the primary particles of the metallic nickel particles are not monodispersed but are generated in a significantly aggregated state, or the shape of the secondary particles is It is agglomerate, and the size and shape are uneven. As a result, there is a problem that defects having poor fillability are likely to occur when a circuit, an electrode, or the like in which the resulting metal nickel fine particles are not sufficiently dispersible in the fluid composition are formed, resulting in a multilayer ceramic capacitor. It is difficult to cope with the thinning of one internal electrode and the miniaturization of printed circuit boards. Accordingly, there is a demand for fine metal nickel particles that are fine but have a uniform particle shape with almost no aggregated particles and excellent dispersibility.
  • the inventors of the present invention have intensively studied focusing on a method for reducing the nickel compound as a raw material to solve these problems.
  • the medium liquid contains at least a protective colloid, a reducing agent, and a nickel compound that is hardly soluble in the liquid medium.
  • the present inventors have found that fine nickel particles having a uniform primary particle size, a monodispersed and almost uniform aggregated particle shape, and a uniform particle shape can be obtained.
  • the present invention provides: (1) The average particle diameter (D) measured with an electron microscope is in the range of 0.001 to 0.5 / m, and the average particle diameter (d) calculated from the specific surface area is 0.001 to 0.5 / im. And nickel fine particles having a d / D in the range of 0.85 to 1.30,
  • a fluid composition characterized by containing at least the nickel fine particles and the dispersion medium of (1).
  • the nickel fine particles obtained by the method of the present invention are fine, hardly contain aggregated particles, have a uniform particle shape, and are excellent in dispersibility.
  • This material is useful as an electrode material for electronic equipment, and the nickel fine particles are used as a fluid composition to produce, for example, an internal electrode of a multilayer ceramic capacitor, a circuit of a printed wiring board, and other electrodes. Then, a high-density electrode etc. are obtained with a smooth thin film.
  • the present invention is a method for producing nickel fine particles, comprising at least a protective colloid, a reducing agent, and a nickel compound that is hardly soluble in a liquid medium, followed by aging, Including a second step of adding at least one selected from a noble metal and its compound and a reducing agent to the liquid after the step, wherein about 70% or more of the sparingly soluble nickel compound comprises the first step and the second step. And finally reduced to metallic nickel.
  • the first step is a step in which at least a protective colloid, a reducing agent, and a nickel-compound that is hardly soluble in the liquid medium are mixed and contained in the liquid medium, and ripened.
  • This is a pre-process for producing metallic nickel with small crystallites that can be crystallized, or adjusting the solubility of the hardly soluble nickel compound by the solvent composition or the like.
  • the raw material to be used is mixed with a liquid medium.
  • the temperature of the mixed liquid at that time may be in the range of 10 ° C to the boiling point of the used liquid, but in the range of 40 to 95 ° C when the boiling point of the medium is about 100 ° C or higher. 60-95 because it is easy to obtain nickel micronuclear crystals
  • the range of 80 ° C is more preferable.
  • the range of 80 to 95 ° C is more preferable.
  • the mixing time in the first step can be set by controlling the addition time of raw materials such as a reducing agent and protective colloid, and for example, about 10 minutes to 6 hours is appropriate.
  • the reducing agent In the first step, it is preferable to add the reducing agent after first adding the hardly soluble nickel compound and the protective colloid to the medium. If significant foaming is observed when the reducing agent is added, an antifoaming agent such as silicone, polyacrylic, polyvinylic, fluorine or wax may be used. In addition, it is preferable to add a complexing agent, which will be described later, to facilitate control of the particle size distribution and particle shape.
  • an antifoaming agent such as silicone, polyacrylic, polyvinylic, fluorine or wax may be used.
  • a complexing agent which will be described later, to facilitate control of the particle size distribution and particle shape.
  • the aging temperature is preferably 40 ° C or more, more preferably in the range of 40 to 95 ° C, more preferably in the range of 60 to 95 ° C, and still more preferably in the range of 80 to 95 ° C. It is industrially preferable to perform the reaction and aging in the first step at the same temperature.
  • the aging time is preferably in the range of 5 minutes to 2 hours, more preferably in the range of 10 minutes to 1 hour.
  • the amount of metal nickel micronuclear crystals produced in the first step can be adjusted as appropriate depending on the type of reducing agent, the temperature of the medium, the temperature of aging, the time, and the like.
  • the formation rate of metallic nickel micronuclear crystals in this process is: (the amount of metallic nickel produced in the first step by X-ray diffraction) / (theoretical amount of metallic nickel calculated from the amount of Nikkenole compound in the raw material) X 100 (% 0 to 50% by weight is preferred, and about 0 to 30% by weight is more preferred. 0 to about 10% by weight is more preferred.
  • the metal nickel micronuclear crystal is too fine, and its formation is not confirmed by X-ray diffraction. On the other hand, if the production rate is higher than 50% by weight, aggregated particles that are difficult to control the reduction reaction are easily produced, which is not preferable.
  • an aqueous or organic solvent medium such as alcohol
  • an aqueous medium is preferably used.
  • An aqueous medium liquid is an aqueous solvent or a mixed medium liquid of water mainly composed of water and a hydrophilic organic solvent. In this case, water is usually a mixed medium. If the liquid contains 50% by weight or more, preferably 80% by weight or more, it is good.
  • the “slightly soluble nickel compound” is one that does not completely dissolve when added to a room temperature medium at a predetermined reaction rate, and is about 50% by weight or more, preferably about 75% by weight or more of the amount added. More preferably, about 90% by weight or more, more preferably about 95% by weight or more remains as a solid content. If an aqueous medium is used as the medium, nickel carbonate, nickel oxide, nickel hydroxide, nickel phosphate, nickel sulfide, nickel carbonyl and the like can be used. In the present invention, the rate of the reduction reaction is controlled by using a poorly soluble compound in the nickel compound. When a highly soluble nickel compound is used, the nickel ion elutes all at once and contacts with the reducing agent.
  • the reduction reaction proceeds, and a large amount of metallic nickel microcrystals are distributed in a non-uniform concentration distribution. Generate. For this reason, the particle growth also becomes uneven, the shape of the nickel fine particles becomes uneven, and the generation of aggregated particles cannot be suppressed. Since the hardly soluble nickel compound reacts with the reducing agent as it is gradually dissolved in the liquid medium, the reduction reaction can be easily controlled. For this reason, when water is used as the medium, it is preferable that the solubility in 100 g of water at 25 ° C. is in the range of 0.001-0.lg. Examples of such hardly soluble nickel compounds include nickel carbonate. For nickel carbonate, any known power of basic salt, acid salt, and normal salt can be used without limitation.
  • the solubility of the nickel compound when it is necessary to improve the solubility of the nickel compound, it can be adjusted by using an acid, an alkali, an organic solvent, or the like, or by heating.
  • the “protective colloid” used in the first step acts as a dispersion stabilizer for the formed metal nickel micronuclear crystals, and prevents aggregation of the formed micronuclear crystals.
  • the protective colloid known ones can be used. For example, gelatin, gum arabic, casein, strength protein such as sodium zelate, ammonium caseinate, etc., natural high concentrations such as starch, dextrin, agar, sodium alginate, etc.
  • sulreloses such as hydroxyethyl cellulose, carboxymethylenosenorose, methinoresenorelose, ethinoresenololose, butyls such as polyvinyl alcohol and polybutylpyrrolidone, poly (sodium acrylate), poly (poly (allyl) acid)
  • acrylic acid such as ammonium
  • synthetic polymers such as polyethylene glycol. One or more of these may be used.
  • High molecular protective colloid Since the effect of stabilization is high, when reacting in an aqueous medium where it is preferable to use this, it is preferable to use a water-soluble one, especially gelatin, polybutyl alcohol, polyvinyl pyrrolidone, and polyethylene glycol. preferable.
  • a water-soluble one especially gelatin, polybutyl alcohol, polyvinyl pyrrolidone, and polyethylene glycol. preferable.
  • the amount used is in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the nickel compound, the range of 2 to 50 parts by weight is more preferable because the formed micronuclear crystals are easily dispersed and stabilized.
  • a known compound can be used as the “reducing agent” used in the first step.
  • a hydrazine reducing agent ((a) hydrazine or a hydrate thereof, (b) a hydrazine compound) (Eg, hydrazine hydrochloride, hydrazine sulfate, etc.)), (2) hydrogen compounds (eg, sodium borohydride), (3) low-order inorganic oxygen acids (eg, sulfurous acid, nitrous acid, hyponitrous acid, nitrous acid, etc.) Phosphoric acid, hypophosphorous acid, etc.) and their hydrates (eg, bisulfite) or their salts (eg, alkali metal salts such as sodium), (4) aldehydes ((a) aliphatic aldehydes ( For example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyl aldehyde, etc.), (b)
  • the hydrazine reducing agent (1) is preferred because of its strong reduction reactivity.
  • the amount of the reducing agent used is preferably 0.05 to 3.0 range power S, more preferably 0.2 to 2.0 mol, with respect to one monoke of Eckenole contained in the nickel compound. If the amount used is larger than this range, the formation of micronuclear crystals will be non-uniform, and it will be difficult to obtain monodispersed and finely-shaped nickel fine particles, and the subsequent operation will be difficult due to significant foaming. If the amount is too small, the desired state will not be achieved.
  • the production rate of the metallic nickel micronuclear crystals can be within the above range. preferable.
  • the second step is a subsequent step of generating metallic nickel by adding at least one kind selected from a noble metal and its compound power and a reducing agent to the liquid after the first step.
  • the second step is a step of reducing the unreacted Nikkenore compound in the first step to grow micronuclear grains, and the noble metal or the compound acts as a reaction accelerator. The compound can be reduced almost completely.
  • the temperature of the second step can be the same as the temperature of the first step, or the boiling point of the medium can be adjusted to the range of 10 ° C to the boiling point of the medium. If the temperature is about 1 oo ° C or more, it is preferable because the fine nickel fine particles can be obtained in the range of 40 to 95 ° C.
  • the time for the second step can be set by controlling the addition time of raw materials such as a reducing agent, for example, about 10 minutes to 6 hours is appropriate.
  • a reducing agent after first adding at least one selected from precious metals and compounds thereof to the liquid after the first step. If significant foaming is observed when a reducing agent is added, antifoaming agents such as silicones, polyaryls, polybules, fluorines and waxes can be used. Further, it is preferable to add a complexing agent which will be described later because it is easier to control the particle size distribution and particle shape.
  • the protective colloid can be added during the reaction in the second step, if necessary.
  • a slightly soluble nickel compound may be added as appropriate in order to enlarge the generated metal nickel fine particles.
  • the aging temperature is preferably 40 ° C or higher, more preferably in the range of 40 to 95 ° C, more preferably in the range of 60 to 95 ° C, and still more preferably in the range of 80 to 95 ° C. It is industrially preferable that the temperature of the second step and aging are performed at the same temperature.
  • the aging time is preferably in the range of 5 minutes to 2 hours, and more preferably in the range of 10 minutes to 1 hour.
  • the reducing agent used in the second step the reducing agent described in the first step can be used, and since the reduction reactivity is strong, a hydrazine reducing agent ((a) hydrazine or a hydrate thereof, ( b) Hydrazine compounds (for example, hydrazine hydrochloride, hydrazine sulfate, etc.) are preferred.
  • the reducing agent may be added at once, and the unreacted nickel-rich compound may be reduced or divided. In the case of divided addition, the same type of reducing agent can be used, or two or more different types of reducing agents can be used.
  • the amount of reducing agent used should be such that almost all of the Nikkenore compound is reduced, and a range of 0.2 to 5.0 moles per mole of nickel contained in the nickel compound is preferred. That's right. If the amount used is larger than this range, the formation of micronuclear crystals becomes non-uniform, and it is difficult to obtain monodispersed and finely-shaped nickel fine particles, and the subsequent operation becomes difficult due to significant foaming.
  • the amount of unreacted nickel compound can be reduced almost completely if the amount used is at least within the above range. .
  • a more preferable range is 1.0 to 3.0 mol. If two or more reducing agents are used, the total amount is within the above range, and the amount used is appropriately distributed.
  • the precious metal and its compound used in the second step work as a reaction accelerator, and when a hydrazine-based reducing agent is used as the reducing agent, it also acts as a decomposition inhibitor for hydrazine-based compounds. .
  • the metallic nickel acts as a decomposition catalyst for the hydrazine-based reducing agent and inhibits the reduction reaction.
  • noble metals and their compounds suppress the decomposition of the hydrazine-based compound, making it difficult to inhibit the reduction reaction.
  • the noble metal and its compound at least one selected from metals of gold, silver, copper, platinum group elements (ruthenium, rhodium, palladium, osmium, iridium, platinum) and compounds thereof can be used.
  • noble metal compounds include noble metal salts, bromides, sulfates, nitrates, oxides, sulfides, acetates, and complex salts.
  • At least one selected from palladium, gold, platinum and their compounds is preferred because it has a higher effect of addition.
  • the precious metal or compound used is not particularly limited in terms of its properties and size, such as powder or agglomerate, but is preferably easily dispersed or colloidal or easily dissolved in a liquid medium. .
  • the palladium compounds include palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, palladium propionate, palladium oxide, palladium sulfide, palladium hydride, palladium complexes (dinitrodiammine palladium, tetraammine paradichlorodichloride, Tetraamminepalladium dinitrate, tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium, dichloro (1,3-bis (diphenylphosphine) propane) palladium, bis (tricyclohexylphosphine) paradium , Di- ⁇ -Black-mouthed bis (-aryl) palladium, bis (acetylacetonato) palladium, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium ,
  • Gold compounds include gold chloride, gold bromide, gold oxide, gold sulfide, gold complex (halogenated gold acid and its salts, gold cyanide complex, cystinato gold, black mouth (diethylenetriamine) gold salt, [ Bis (2-aminoethyl) amido] chromate, tetraammine gold salt, dioctadecyldimethylammonium bis (1,3-dithiol-2-thione-4,5_dithiolate) gold and the like.
  • Platinum compounds include platinum chloride, platinum oxide, platinum sulfate, platinum nitrate, platinum complexes (halogenated platinic acid and its salts, hydroxoplatinic acid and its salts, tetraammineplatinum dichloride, dinitrodiammineplatinum, bis (pentane-1,2, 4-dione) platinum, tetrakis (thiourea) platinum, bis (acetamidine) diammineplatinum, dichlorobis (oxalato) platinate, bis (tetra-n-butylammonium) bis (1,3 dithiol-2 thione 4,5 dichloro ) Platinum etc.).
  • complexes are preferable because they have a large effect of inhibiting decomposition.
  • the palladium complex it is more preferable that at least one ligand such as dinitrodiammine palladium, tetraamine palladium dichloride, tetraammine palladium dinitrate, etc. is an amine.
  • the gold complex is more preferably chloroauric acid, preferably haloauric acid and its salt.
  • the platinum complex it is more preferable if the halogenated platinic acid and its salt are preferred salts.
  • a noble metal such as palladium metal, gold metal or platinum, or a noble metal compound other than a complex such as palladium chloride, gold chloride or platinum chloride is mixed with a complexing agent described later.
  • a complex may be formed in the second step.
  • the amount of precious metal and its compound used is preferably 0.0 :! to 2 parts by weight in terms of precious metal with respect to 100 parts by weight of the reducing agent used in the second step. The range of parts by weight is even better.
  • the first step and / or the second step be carried out in the presence of a complexing agent because it is easier to control the particle size distribution and particle shape.
  • the complexing agent is a nickel compound that elutes nickel ions from the nickel compound or the nickel oleore compound and reduces the nickel metal content.
  • Examples of the donor atom possessed by the “complexing agent” include nitrogen, oxygen, sulfur and the like.
  • Complexing agents in which nitrogen is a donor atom include (a) amines (for example, primary amines such as ptylamine, ethynoleamine, propylamine, and ethylenediamine, dibutylamine, jetinoamine, dipropylamine, and piperidine. Secondary amines such as imines such as pyrrolidine, tertiary amines such as tribubutanolamine, triethylamine, tripropylamine, etc., 1 to tertiary amine in one molecule of jethylenetriamine and triethylenetetramine.
  • amines for example, primary amines such as ptylamine, ethynoleamine, propylamine, and ethylenediamine, dibutylamine, jetinoamine, dipropylamine, and piperidine. Secondary amines such as imines such as pyrrolidine, tertiary amines such as tribubutanolamine, trie
  • (B) Nitrogen-containing heterocyclic compounds eg, imidazole, pyridine, bipyridine, etc.
  • (d) Anne Mona and ammonium compounds eg, ammonium chloride, ammonium sulfate, etc.
  • (2) Complexing agents in which oxygen is a donor atom include (a) carboxylic acids (for example, oxycarboxylic acids such as citrate, lingoic acid, tartaric acid and lactic acid, monocarboxylic acids such as acetic acid and formic acid, oxalic acid, Dicarboxylic acids such as malonic acid, aromatic carboxylic acids such as benzoic acid, etc.), (b) ketones (eg monoketones such as acetone, diketones such as acetylacetone and benzoylacetone), (c) Aldehydes, (d) alcohols (monohydric alcohols, glycols, glycerols, etc.), (e) quinones, (f) ethers, (g) phosphoric acid (normal phosphoric acid) and phosphoric acid compounds (For example, hexametaphosphoric acid, pyrophosphoric acid, phosphorous acid, hypophosphorous acid, etc.), (h) sulfonic acid
  • Complexing agents in which sulfur is a donor atom include (a) aliphatic thiols (for example, methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, ⁇ -butyl mercaptan, aryl mercaptan) , Dimethyl mercaptan, etc.), (b) alicyclic thiols (such as cyclohexenolethiol), (c) aromatic thiols (such as thiophenol), (d) thioketones, (e) thioethers, (f) Polythiols, (g) thiocarbonates (trithiocarbonates), (h) sulfur-containing heterocyclic compounds (eg, dithiols, thiophenes, Opiran, etc.), (thiocyanates and isothiocyanates, (j) inorganic sulfur compounds (for example, sodium sulfide
  • Complexing agents having two or more types of donor atoms include: (a) amino acids (donor atoms are nitrogen and oxygen: for example, neutral amino acids such as glycine and alanine, bases such as histidine and arginine) Amino acids, acidic amino acids such as aspartic acid and glutamic acid), (b) amino polycarboxylic acids (donor atoms are nitrogen and oxygen: for example, ethylenediaminetetraacetic acid (EDTA), ditrimethyl triacetic acid (NTA), iminodiacetic acid (IDA), ethylenediaminediacetic acid (EDDA), ethylene glycol jetyl ether diaminetetraacetic acid (GEDA), etc.) (c) alkanolamines (the donor atom is nitrogen and oxygen: for example, ethanolamine, (Tanolanolamine, triethanolamine, etc.), (d) Nitro compounds, nitroso compounds and nitrosyl compounds (donor atoms are nitrogen and oxygen) (E) amino
  • salts and derivatives of the above-mentioned compounds include, for example, alkali metal salts such as trisodium citrate, sodium potassium tartrate, sodium hypophosphite, disodium ethylenediaminetetraacetate, and carboxylic acids. And esters such as phosphoric acid and sulfonic acid.
  • complexing agents at least one kind can be used, and among them, alkenol amine is preferred because it easily forms a complex with nickel ions or metallic nickel.
  • carboxylic acids are easy to form complexes with noble metals and their compounds.
  • the amount of the complexing agent used can be set as appropriate. In each of the first step and the second step, complexing occurs when the Nikkenore compound is set in the range of 0.01 to 150 parts by weight per 100 parts by weight. Since the effect of the agent is easily obtained, it is preferable. Within the above range, if the use amount of the complexing agent is reduced, the primary particle size of the nickel fine particles can be reduced, and if the use amount is increased, the primary particle size can be increased. A more preferred dosage is in the range of 0.1 to 100 parts by weight.
  • the order of addition of the respective raw materials is not limited.
  • the method (3) is particularly preferable because the methods (2) and (3) are preferable because the reaction is easily controlled.
  • “Simultaneous parallel addition” refers to a method in which raw materials are added separately at the same time during the reaction period. In addition to adding both continuously during the reaction period, one or both are intermittently added. It may be added to the product.
  • the second step (I) a method in which at least one selected from a noble metal and its compound is added to the liquid after the first step, and then a reducing agent is added; (II) the first step A method in which a complexing agent is added to the subsequent liquid before, during or after the addition of the noble metal or its compound, and then a reducing agent is added; (III) the liquid after the first step And a method of adding a reducing agent after adding the mixed solution of the noble metal or its compound and a complexing agent. Since the complexing agent also acts as a raw material for the complex as described above, when the metal compound other than the metal complex is used, the method (III) is preferable because the complex is easily formed.
  • the separation means such as gravity filtration, pressure filtration, vacuum filtration, suction filtration, centrifugal filtration, and natural sedimentation, but industrially preferred are pressure filtration, vacuum filtration, and suction filtration. Therefore, it is preferable to use a filter such as a filter press or a roll press.
  • a filter such as a filter press or a roll press.
  • the flocculant As the flocculant, known ones can be used. Specifically, anionic flocculants (for example, polyacrylamide partial hydrolysis products, acrylamide'sodium acrylate copolymer, sodium alginate, etc.), Cationic flocculants (eg, polyacrylamide, dimethylenoethyl acetylmethacrylate, dimethylaminoethyl acrylate, polyamidine, chitosan, etc.), amphoteric flocculants (eg, acrylamide 'dimethylaminoethyl acrylate / acrylic acid copolymer, etc.) ) And the like.
  • the addition amount of the flocculant can be appropriately set according to need.
  • the range of 0.5 to 100 parts by weight is preferable with respect to 1000 parts by weight of the nickel fine particles, and the range of 1 to 50 parts by weight is preferable. Further preferred.
  • a protective colloid remover may be added to the medium to remove the protective colloid to aggregate the nickel fine particles, and then separate.
  • Protective colloid remover is a compound that decomposes or dissolves the protective colloid to suppress the action of the protective colloid. If the liquid protective colloid cannot be completely removed, it can be removed. An effect is obtained.
  • the type of protective colloid remover is appropriately selected according to the protective colloid used.
  • serine protease eg, trypsin, chymotrypsin, etc.
  • thiol protease eg, papain, etc.
  • acidic protease eg, pepsin, etc.
  • metalloprotease etc.
  • Proteolytic enzymes can be used, starch-degrading enzymes such as amylase and maltase can be used for starch systems, and cellulose-degrading enzymes such as cellulase and cellobiase can be used for cellulose systems.
  • protective colloids such as bulle, acrylic acid, and polyethylene glycol
  • organic solvents such as honolemamide, glycerin, and glycol, acids, alkalis, and the like can be used.
  • the amount of protective colloid remover added depends on the type of protective colloid, as long as it can remove nickel so that it can aggregate and separate nickel particles. On the other hand, the force in the range of 0.001 to 1000 lbs. S is preferred ⁇ , 0.01 to 200 Part by weight is more preferred 0.01-: More preferably 100 parts by weight.
  • the temperature of the medium at the time of adding the protective colloid remover can be set as appropriate, and the reduction reaction temperature may be maintained or it may be within the range of 10 ° C to the boiling point of the medium used.
  • the temperature is in the range of 40 to 95 ° C.
  • the protective colloid can be decomposed if the state is appropriately maintained. For example, about 10 minutes to 10 hours is appropriate.
  • After removing the protective colloid preferably adjust the pH or add an aggregating agent, and then sort by the usual method.
  • the obtained solid particles of the nickel fine particles are used, for example, dispersed in an organic solvent medium such as aqueous or alcohol, preferably in an aqueous medium.
  • an organic solvent medium such as aqueous or alcohol
  • the solid matter of nickel fine particles may be dried by a usual method, and after further drying, it may be used, for example, in an aqueous solvent or an organic solvent medium such as alcohol, preferably dispersed in an aqueous medium.
  • pulverization may be performed as necessary.
  • the nickel powder is heated to a temperature of 200 to 1200 ° C in a reducing atmosphere such as hydrogen or in an inert atmosphere such as nitrogen or argon.
  • a sintering inhibitor such as an alkali metal salt or an alkaline earth metal salt may be mixed with the nickel powder.
  • the present invention is a nickel fine particle having a metallic substance containing at least metallic nickel, and contains impurities or the like on the surface of the nickel fine particle or inside thereof to such an extent that it does not interfere with the use. It may also contain components such as the aforementioned raw materials.
  • the nickel fine particles of the present invention are fine, hardly contain aggregated particles, and have a uniform particle shape.
  • the nickel fine particles of the present application have an average particle diameter (cumulative 50./. Diameter) (D) in the range of 0.001 to 0.5 xm by electron microscopy, and the shape of the nickel fine particles is truly spherical.
  • the average particle diameter (d) obtained from the following formula using the specific surface area is in the range of 0.001-0. 5 zm, and the dZD is in the range of 0.85 to 1.30. It is.
  • p is the specific gravity of metallic nickel and is 8.9 g / cm 3 .
  • S is the specific surface The product value (m 2 / g). The specific surface area is determined by nitrogen adsorption based on the BET method.
  • the average particle size (D), (d) is fine within the above range, and d / D is very close to 1 within the above range, so the degree of aggregation is low.
  • the dispersibility in the fluid composition is excellent.
  • Such nickel fine particles can be obtained by the production method described above.
  • d / D may be smaller than d / D force S1 because the measurement method of force (D) and (d), which normally takes a value of 1 or more, is different.
  • the shape of the nickel fine particles of the present invention can be observed with an electron microscope, and has a spherical or substantially spherical particle shape.
  • the preferred range for (D) is 0.01 to 0.3 zm
  • the preferred range for (d) is 0.01 to 0.3 xm
  • the preferred d / D range the range f to 0.85 to 1. 2.
  • the present invention is a fluid composition such as ink, paint, paste, and the like, and contains at least the nickel fine particles and the dispersion medium.
  • the amount of nickel fine particles should be at least about 1% by weight, preferably a high concentration of 5% by weight or more, more preferably 10% by weight or more, and even more preferably 15% by weight or more.
  • the dispersion medium for dispersing the nickel fine particles is appropriately selected according to the affinity with the nickel fine particles to be used.
  • hydrophilic organic solvents such as water solvents, alcohols, and ketones
  • linear hydrocarbons such as hydrocarbons and aromatic hydrocarbons
  • cyclic Hydrophobic organic solvents such as hydrocarbons and aromatic hydrocarbons
  • water and a hydrophobic organic solvent can be mixed and used using a hydrophilic organic solvent as a compatibilizing agent.
  • alcohols include methanol, ethanol, propynole alcohol, isopropyl alcohol, butanol, isobutanol, and monoterbinol.
  • ketones include cyclohexanone, methylcyclohexanone, and 2-butanone.
  • a preferable dispersion medium used for inks and paints is an aqueous solvent or a mixed dispersion medium with a hydrophilic organic solvent mainly composed of water.
  • water is usually 50% by weight or more in the mixed dispersion medium. , Preferably 80 weight If it is contained more than%.
  • the relative permittivity is 35 or more, preferably in the range of 35 to 200, as necessary.
  • an organic solvent having a boiling point of 100 ° C or higher, preferably 100 to 250 ° C is added, a uniform and high density is obtained in which surface defects such as shrinkage are not easily generated during heating and baking. It is preferable because a coated product is easily obtained.
  • N_methylformamide (dielectric constant 190, boiling point 197 ° C), dimethyl sulfoxide (relative dielectric constant 45, boiling point 189 ° C), ethylene glycol (relative dielectric constant 38, boiling point 226 ° C) ), 4_Butyloraton (relative permittivity 39, boiling point 204 ° C), acetoamide (relative permittivity 65, boiling point 222 ° C), 1,3 dimethyl-2-imidazolidinone (relative permittivity 38, boiling point 226 ° C) , Formamide (dielectric constant 111, boiling point 210 ° C), N-methylacetamide (dielectric constant 175, boiling point 205 ° C), furfural (dielectric constant 40, boiling point 161 ° C), etc.
  • N-methylformamide (surface tension 38 X 10 _3 N / m), surface tension of 50 X 10 _3 N / m or less, dimethyl sulfoxide (surface tension 43 X 10 _3 N / m), ethylene glycol (surface tension 48 X 10 " 3 N / m), 4 Butyrolatatone (surface tension 44 X 10" 3 N / m), Acetamide (surface tension 39 X 10 _3 N / m), 1, 3 Dimethyl-2 imidazolidinone (surface tension 41 X 10 — 3 N / m) and the like are more effective and preferable.
  • These organic solvents having a high relative dielectric constant and a high boiling point are preferably contained in the dispersion medium excluding water in the range of 20 to 100% by weight, and more preferably in the range of 40 to 100% by weight.
  • additives such as a surfactant, a dispersant, a thickener, a plasticizer, and an antifungal agent are appropriately blended in the fluid composition of the present invention. You can also.
  • the surface active agent has the effect of further improving the dispersion stability of the nickel fine particles and the rheological properties of the flowable composition to improve the coatability.
  • a quaternary ammonium salt is used.
  • Cationic salts such as carboxylic acid salts, carboxylate salts, sulfonate salts, sulfate ester salts, phosphoric acid ester salts, and other nonionic materials such as ether types, ether ester types, ester types, and nitrogen-containing types are used. One or more selected from these can be used.
  • the compounding amount of the surfactant is set appropriately according to the coating composition. Generally, the range of 0.01 to 0.5 parts by weight is 1 part by weight of nickel fine particles. I like it.
  • Organic curable binders such as cellulose resins such as resins, furan resins, urea resins, polyurethane resins, melamine resins, silicone resins, and ethyl cellulose may be contained.
  • the amount of the curable binder can be set as appropriate according to the usage situation. When forming an electrode or wiring pattern, the curable binder is not added, or 0 to 0.5% by weight based on 1 part by weight of the nickel fine particles. A range of about is suitable, and a range of 0 to 0.1% by weight is more suitable.
  • the flowable composition of the present invention can be produced by mixing nickel fine particles and a dispersion medium and further other additives by a known method. For example, wet mixing such as stirring and mixing, colloid mill, etc. A method such as pulverization and mixing can be used.
  • the fluid composition obtained in this way can be used for various applications, for example, by applying it to a substrate by a method such as screen printing or ink jet printing, followed by heating and baking, and a circuit of a printed wiring board, It can be used as other fine conductive members.
  • Example 2 In the first step of Example 1, 0.24 g of monoethanolamine as a complexing agent and hydrazine monohydrate as a reducing agent were simultaneously added to the mixed solution of nickel carbonate and gelatin. Except for this, in the same manner as in Example 1, nickel fine particles (sample B) of the present invention were obtained. It was confirmed that almost all of Sample B was metallic nickel.
  • Example 2 nickel fine particles (sample C) of the present invention were obtained in the same manner as in Example 2 except that the amount of monoethanolamine used was 0.48 g.
  • Example 2 in place of palladium dinitrodiammine, 0.012 mol / Lit Nore metal palladium colloid (particle diameter 20 nm) was added in the same manner as in Example 2 except that 14 ml of metal palladium colloid (particle diameter 20 nm) was added. Sample D) was obtained.
  • the first step was used in the same manner as in Example 1 and the second step described below. (Second process)
  • the solution after the first step was added to a 0.01 mol / liter palladium chloride solution 12 mm.
  • nickel nickel carbonate fine particles were produced by reacting until nickel carbonate was completely disappeared.
  • Example 1 nickel fine particles (sample F) of the present invention were obtained in the same manner as in Example 1 except that tetrachlorophthalic acid was used instead of palladium dinitrodiammine.
  • Nickel microparticles (sample G) of the present invention were obtained in the same manner as in Example 1 except that hexachloroplatinic acid was used instead of palladium dinitrodiammine in Example 1. It was confirmed that almost all of Sample G was metallic nickel.
  • the first step was used in the same manner as in Example 1 and the second step described below. (Second process)
  • This sample I was confirmed to contain unreacted nickel carbonate in addition to metallic nickel.
  • Nickel carbonate l lg was added to 200 ml of pure water, mixed, heated to 90 ° C, and then stirred, 33.3 g of 60% hydrazine monohydrate (4.5 moles per mole of nickel) And then aged by holding for 2 hours while maintaining a temperature of 90 ° C. Thereafter, filtration and washing were performed in the same manner as in Comparative Example 1 and drying was performed, so that Sample J for comparison was obtained.
  • the first step was performed in the same manner as in Comparative Example 3 except that the concentration of the palladium chloride aqueous solution used in the first step of Comparative Example 3 was 0.1 mol / liter. Then same as Comparative Example 3 Then, when the second step was performed, when Nikkenore sulfate and hydrazine monohydrate were added, foaming occurred, and the reaction was continued until foaming subsided. Next, filtration, washing, and drying were performed in the same manner as in Comparative Example 1 to obtain comparative nickel fine particles (sample K).
  • this sample K contained unreacted nickel sulfate in addition to metallic nickel.
  • Nickel chloride (47.59g) as a water-soluble nickel compound, gelatin (1.18g) as a protective colloid, and ammonia water (90milliliter) were mixed with 250 milliliters of pure water, mixed and heated to 90 ° C. Then, with stirring, 8.39 g of 60% hydrazine monohydrate (0.5 mol with respect to 1 mol of nickel) was added all at once, and aged for 30 minutes.
  • Comparative Example 1 2 4 5 The average particle size (D) of the sample AL obtained in 5 was measured by electron microscopy, and the average particle size (d) was measured using a specific surface area measuring device (micromeritics flow method). It was calculated from the BET specific surface area measured with a tube 2300 (manufactured by SHIMADZU). The results are shown in Table 1.
  • the nickel fine particles obtained from the present invention have fine average particle diameter (D) and average particle diameter (d), and d / D is close to 1, indicating that almost no aggregated particles are contained.
  • Comparative Example 1 2 4 5 In the yield of nickel fine particles (the obtained two The amount of nickel particles / theoretical amount of nickel metal calculated from the raw material Nikkenore compound) X 10 0 (%). The results are shown in Table 1. In Comparative Examples 2, 4, and 5, it was difficult to separate the nickel fine particles from the unreacted nickelore compound, and measurement was not possible. From this result, it can be seen that the production method of the present invention has a high yield. Among them, the method of Example 8, that is, the method of adding sodium hypophosphite after adding hydrazine in the second step was particularly excellent in yield.
  • Example 8 and Comparative Example 1 Samples H and I synthesized in Example 8 and Comparative Example 1 were kneaded with three rolls having the composition shown in Table 2 and pasty. Apply the resulting paste to a PET film with a 2mil applicator. It was dried at 0 ° C for 1 hour to obtain a dried coating film.
  • the surface roughness Ra of these dried coating films was calculated according to the “arithmetic average roughness” of JIS B0601 (1994) using an ultra-deep shape measuring microscope (VK-8550: manufactured by KEYEN CE). Table 3 shows the results obtained. From this result, it was found that the dry coating film using the nickel fine particles of the present invention was smooth with a small surface roughness Ra as compared with the comparative example. This is considered to be because the dispersibility of the nickel fine particles of the present invention when the paste is made with less aggregated particles is excellent.
  • the nickel fine particles of the present invention are useful as electrode materials for electronic devices, and are particularly useful for internal electrodes of multilayer ceramic capacitors, circuits of printed wiring boards, and other electrodes.
  • FIG. 1 is an electron micrograph (magnification: 20,000 times) of the nickel fine particles (sample A) obtained in Example 1.
  • FIG. 2 shows an electron micrograph of the nickel fine particles (sample B) obtained in Example 2 (magnification 2). Million times).
  • Fig. 3 is an electron micrograph (magnification 20,000 times) of the nickel fine particles (sample C) obtained in Example 3.
  • Fig. 4 is an electron micrograph (magnification of 20,000 times) of the nickel fine particles (sample D) obtained in Example 4.
  • FIG. 5 is an electron micrograph (magnification of 20,000 times) of the nickel fine particles (sample E) obtained in Example 5.
  • FIG. 6 is an electron micrograph (magnification of 20,000 times) of the nickel fine particles (sample F) obtained in Example 6.
  • Fig. 7 is an electron micrograph (magnification 20,000 times) of the nickel fine particles (sample G) obtained in Example 7.
  • FIG. 8 is an electron micrograph (magnification of 20,000 times) of the nickel fine particles (sample H) obtained in Example 8.
  • Figure 9 is an electron micrograph (magnification 20,000 times) of the nickel fine particles (sample I) obtained in Comparative Example 1.
  • Figure 10 is an electron micrograph (magnification 20,000 times) of the nickel fine particles (sample J) obtained in Comparative Example 2.
  • FIG. 11 is an electron micrograph (magnification of 20,000 times) of the nickel fine particles (sample K) obtained in Comparative Example 4.
  • Fig. 12 is an electron micrograph (magnification 20,000 times) of the nickel fine particles (sample L) obtained in Comparative Example 5.

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Abstract

L'invention concerne un procédé de fabrication de fines particules métalliques de nickel par réaction d'un composé du nickel avec un agent réducteur dans un milieu liquide. Dans ce procédé, un milieu liquide est additionné d'au moins un colloïde protecteur, d'un agent réducteur et d'un composé du nickel faiblement soluble dans le milieu liquide; le liquide résultant est vieilli, puis un agent réducteur et au moins une substance choisie parmi les métaux nobles et leurs composés sont ajoutés dans le liquide vieilli, permettant ainsi d'obtenir de fines particules métalliques de nickel. En tant que métaux nobles et leurs composés, au moins une substance choisie parmi le palladium, l'or, le platine et leurs composés est préférable. Les fines particules métalliques de nickel ainsi obtenues ont un diamètre moyen de particule (D) tel que mesuré au microscope électronique de 0,001-0,5 μm et un diamètre moyen de particule (d) tel que calculé à partir de la surface spécifique de 0,001-0,5 μm. La valeur de d/D se situe dans la plage de 0,85-1,30. Les fines particules métalliques de nickel sont très fines mais de forme régulière et ne contiennent guère de particules agglomérées. En conséquence, les fines particules métalliques de nickel sont utiles comme matière d'électrode pour des dispositifs électroniques et similaires.
PCT/JP2007/062741 2006-06-27 2007-06-26 Fines particules de nickel, procédé de fabrication de celles-ci, et composition fluide les utilisant Ceased WO2008001741A1 (fr)

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WO2012124625A1 (fr) * 2011-03-17 2012-09-20 新日鐵化学株式会社 Nanoparticules de nickel composite et leur procédé de production
KR20150011573A (ko) * 2013-07-23 2015-02-02 삼성전기주식회사 내부 전극용 니켈 분말, 이를 포함하는 적층 세라믹 커패시터 및 전자부품이 실장된 회로기판
WO2015122315A1 (fr) * 2014-02-17 2015-08-20 住友金属鉱山株式会社 Procédé de production de germe utilisé dans la production de poudre de nickel à teneur réduite en hydrogène
WO2015159846A1 (fr) * 2014-04-15 2015-10-22 住友金属鉱山株式会社 Procédé de production de poudre de nickel ayant une faible concentration de carbone et une faible concentration de soufre
WO2017069067A1 (fr) * 2015-10-19 2017-04-27 住友金属鉱山株式会社 Procédé de production de poudre de nickel
JP2017150073A (ja) * 2016-02-25 2017-08-31 住友金属鉱山株式会社 ニッケル粉末の製造方法
JP2017150074A (ja) * 2016-02-25 2017-08-31 住友金属鉱山株式会社 ニッケル粉末の製造方法
JP2017189771A (ja) * 2017-04-28 2017-10-19 エム・テクニック株式会社 微粒子の製造方法
CN116275081A (zh) * 2023-02-15 2023-06-23 丽水新川新材料有限公司 超细镍粉的制备方法及其在车规级陶瓷电容器中的应用
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US10500644B2 (en) 2014-04-15 2019-12-10 Sumitomo Metal Mining Co., Ltd. Method for producing nickel powder having low carbon concentration and low sulfur concentration
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US10850330B2 (en) 2015-10-19 2020-12-01 Sumitomo Metal Mining Co., Ltd. Process for producing nickel powder
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JP2017189771A (ja) * 2017-04-28 2017-10-19 エム・テクニック株式会社 微粒子の製造方法
WO2024150641A1 (fr) * 2023-01-12 2024-07-18 株式会社神戸製鋼所 Poudre de nickel, matériau de revêtement, élément, composition de résine et article moulé en résine
JP2024099157A (ja) * 2023-01-12 2024-07-25 株式会社神戸製鋼所 ニッケル粉末、防カビ剤、塗料、部材、樹脂組成物及び樹脂成形品
JP7543455B2 (ja) 2023-01-12 2024-09-02 株式会社神戸製鋼所 ニッケル粉末、防カビ剤、塗料、部材、樹脂組成物及び樹脂成形品
CN116275081A (zh) * 2023-02-15 2023-06-23 丽水新川新材料有限公司 超细镍粉的制备方法及其在车规级陶瓷电容器中的应用

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