WO2013031670A1 - Dispersant, et composition de nanoparticules métalliques susceptibles de dispersion - Google Patents

Dispersant, et composition de nanoparticules métalliques susceptibles de dispersion Download PDF

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WO2013031670A1
WO2013031670A1 PCT/JP2012/071395 JP2012071395W WO2013031670A1 WO 2013031670 A1 WO2013031670 A1 WO 2013031670A1 JP 2012071395 W JP2012071395 W JP 2012071395W WO 2013031670 A1 WO2013031670 A1 WO 2013031670A1
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tartaric acid
nickel
dispersant
nanoparticles
metal nanoparticle
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PCT/JP2012/071395
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English (en)
Japanese (ja)
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一人 岡村
山田　勝弘
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新日鉄住金化学株式会社
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Priority to JP2013531273A priority Critical patent/JP5906245B2/ja
Publication of WO2013031670A1 publication Critical patent/WO2013031670A1/fr

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    • 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
    • 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
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/002—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/34—Higher-molecular-weight carboxylic acid esters
    • C09K23/36—Esters of polycarboxylic acids

Definitions

  • the present invention relates to a dispersant for suppressing aggregation of metal nanoparticles and a dispersible metal nanoparticle composition.
  • the metal fine particles have physical and chemical characteristics different from those of bulk metals, various materials such as electrode materials such as conductive pastes and transparent conductive films, high-density recording materials, catalyst materials, and ink-jet ink materials are used. It is used for industrial materials.
  • fine metal particles have been made finer to about several tens to several hundreds of nanometers.
  • multilayer ceramic capacitor electrodes are becoming thinner and more multilayered, and as a material for the electrode layers, metal nanoparticles such as nickel nanoparticles are used.
  • the metal nanoparticles used for industrial materials are required to have a particle diameter as small as, for example, less than 150 nm, a uniform particle diameter, and excellent dispersibility.
  • a particle diameter as small as, for example, less than 150 nm
  • a uniform particle diameter e.g., a uniform particle diameter
  • excellent dispersibility e.g., a uniform particle diameter
  • metal nanoparticles tend to aggregate due to an increase in surface energy.
  • an anionic dispersant for example, Patent Document 1 including a fatty acid containing polyvalent carboxylic acid, an unsaturated fatty acid, or the like, a polymer ionic dispersant (for example, Patent Document 2), phosphate ester compounds (for example, Patent Document 3) and the like are known.
  • Patent Document 1 an anionic dispersant
  • Patent Document 2 a polymer ionic dispersant
  • Patent Document 3 phosphate ester compounds
  • these dispersants can achieve a certain degree of dispersion effect, with the progress of micronization, it is not possible to sufficiently suppress the aggregation of metal fine particles of about several tens to several hundreds of nanometers. It is. Accordingly, there is a demand for a dispersant exhibiting high dispersibility corresponding to the micronization of metal nanoparticles.
  • metal nanoparticles can be obtained by solid phase reaction or liquid phase reaction.
  • solid phase reactions include chemical vapor deposition of nickel chloride and thermal decomposition of nickel formate.
  • a nickel salt such as nickel chloride is directly reduced with a strong reducing agent such as sodium borohydride, a reducing agent such as hydrazine is added in the presence of NaOH, and the precursor [Ni (H 2 NNH 2 2 ] Method of thermal decomposition after forming SO 4 ⁇ 2H 2 O, Method of hydrothermal synthesis by putting nickel complex such as nickel chloride and nickel complex containing organic ligand into pressure vessel with solvent, nickel formate
  • a reducing agent such as a primary amine to a salt or nickel acetate salt and irradiating with microwaves.
  • nickel particles are kneaded in a vehicle, and cationic dispersants and nonionic dispersions are prepared at a predetermined timing.
  • a nickel paste was prepared by adding and dispersing a dispersing agent such as an agent and a zwitterionic system.
  • this production method includes agglomerated nickel particles, coating with a dispersant is performed in the agglomerated state, and a sufficient dispersion effect cannot be obtained.
  • Patent Document 4 a method has also been proposed in which nickel powder is pulverized using a jet mill or a high-pressure homogenizer, and an organic solvent and a saturated fatty acid are added and dispersed in the organic solvent.
  • Patent Document 4 a method has also been proposed in which nickel powder is pulverized using a jet mill or a high-pressure homogenizer, and an organic solvent and a saturated fatty acid are added and dispersed in the organic solvent.
  • Patent Document 5 a technique for obtaining nickel nanoparticles by mixing a nickel precursor, an organic amine, and a reducing agent and then heating is disclosed (Patent Document 5). According to this technique, it is said that the control of the size and shape of nickel nanoparticles is easy. Although the reason is not certain, it is mentioned that the dispersibility in an organic solvent is excellent because nickel nanoparticles are coated with an organic amine. However, when a strong reducing agent is used in this production method, it is difficult to control the reaction, and nickel nanoparticles having a high degree of dispersibility are not necessarily obtained suitably. On the other hand, when a reducing agent having a weak reducing power is used, it is necessary to heat to high temperature in order to reduce nickel metal having a negative oxidation-reduction potential, and accordingly, reaction control is required.
  • a step of adding a reducing agent, a dispersant, and a nickel salt to the polyol solution to produce a mixed solution, a step of stirring and heating the mixed solution, and a step of reacting the mixed solution to produce nickel nanoparticles And the manufacturing method of the nickel nanoparticle containing is disclosed (patent document 6).
  • the reducing agent uses a strong reducing agent as described above, it is said that nickel nanoparticles having a uniform particle size and excellent dispersibility can be obtained without aggregation.
  • the dispersant a cationic surfactant, an anionic surfactant, a cellulose derivative and the like are described.
  • An object of the present invention is to provide a dispersant capable of effectively dispersing metal nanoparticles.
  • the dispersant of the present invention comprises a tartaric acid derivative represented by the following general formula (I).
  • the groups R 1 and R 2 each independently represent an optionally substituted phenyl group.
  • the optionally substituted phenyl group may be a phenyl group, a phenyl group optionally substituted with an alkyl group, or a phenyl group optionally substituted with an alkoxy group.
  • the phenyl group which may be substituted is preferably a phenyl group, a tolyl group or an anisoyl group.
  • the tartaric acid derivative represented by the above general formula (I) is dibenzoyl-D-tartaric acid, dibenzoyl-L-tartaric acid, di-p-toluoyl-L-tartaric acid, di-p-toluoyl-D.
  • the dispersant of the present invention may be used for dispersing metal nanoparticles.
  • the dispersible metal nanoparticle composition of the present invention contains metal nanoparticles and any one of the above dispersants.
  • the metal nanoparticle may have a particle size of 150 nm or less.
  • the metal nanoparticle may be at least one selected from the group consisting of gold, silver, platinum, copper, nickel, titanium, and cobalt.
  • the dispersible metal nanoparticle composition of the present invention may further contain a solvent.
  • the solvent may be an alcohol solvent.
  • the metal nanoparticle may be a nickel nanoparticle obtained by microwave irradiation in a liquid phase.
  • the nickel nanoparticles contain oxygen atoms in the range of 0.5 to 5.0% by mass and carbon atoms in the range of 0.1 to 5.0% by mass. There may be.
  • the dispersant of the present invention for example, even for fine metal nanoparticles having a particle size of 150 nm or less, aggregation is suppressed and an aggregate of metal nanoparticles having a sharp particle size distribution in which single particles are dispersed is obtained. Can do. Further, since the dispersant of the present invention has a strong aggregation suppressing action on metal nanoparticles, an excellent dispersion effect can be expected even with a small amount.
  • the dispersant is composed of a tartaric acid derivative represented by the above general formula (I).
  • the phenyl group which may be substituted in the general formula (I) include a phenyl group, a phenyl group which may be substituted with an alkyl group, and a phenyl group which may be substituted with an alkoxy group.
  • the alkyl group for example, a lower alkyl group having 1 to 4 carbon atoms is preferable because it has an excellent dispersion effect, and a methyl group is more preferable.
  • the alkoxy group a lower alkoxy group having 1 to 4 carbon atoms is preferable because it has an excellent dispersion effect, and a methoxy group is more preferable.
  • specific examples of the optionally substituted phenyl group include a phenyl group, an o-, m- or p-tolyl group, or an o-, m- or p-anisoyl group. Among these, an o- Most preferred are m, or p-tolyl groups.
  • tartaric acid derivative represented by the above general formula (I) include dibenzoyl-D-tartaric acid, dibenzoyl-L-tartaric acid, di-p-toluoyl-L-tartaric acid, di-p-toluoyl-D-tartaric acid.
  • Di-o-4-toluoyl-L-tartaric acid di-o-4-toluoyl-D-tartaric acid, di-m-4-toluoyl-L-tartaric acid, di-m-4-toluoyl-D-tartaric acid, di- -P-anisoyl-L-tartaric acid, di-p-anisoyl-D-tartaric acid, di-o-anisoyl-L-tartaric acid, di-o-anisoyl-D-tartaric acid, di-m-anisoyl-L-tartaric acid, di- -M-anisoyl-D-tartaric acid.
  • di-p-toluoyl-L-tartaric acid di-p-toluoyl-D-tartaric acid, di-o-4-toluoyl-L-tartaric acid, di-o-4-toluoyl- having excellent dispersion effect
  • D-tartaric acid di-m-4-toluoyl-L-tartaric acid
  • di-m-4-toluoyl-D-tartaric acid di-m-4-toluoyl-D-tartaric acid.
  • the tartaric acid derivative represented by the above general formula (I) can be used in combination of two or more. Moreover, it can also be used in combination with the dispersing agent which consists of another compound in the range which does not impair the effect of invention.
  • the nanoparticle of a base metal or a noble metal can be mentioned, for example.
  • the base metal include nickel, titanium, cobalt, copper, chromium, manganese, iron, zirconium, tin, tungsten, molybdenum, vanadium, and the like.
  • the noble metal include gold, silver, platinum, palladium, iridium, osmium, ruthenium, rhodium, rhenium and the like.
  • nanoparticles of nickel, titanium, cobalt, copper, gold, silver, platinum and the like are preferable.
  • nanoparticles that can be produced by microwave irradiation in a liquid phase which will be described later, are particularly preferable, and examples thereof include nanoparticles such as nickel, cobalt, copper, gold, silver, and platinum.
  • the metal nanoparticles may contain the above metal elements alone or in combination of two or more, and may contain elements other than metal elements such as hydrogen, carbon, nitrogen and sulfur.
  • An alloy of Furthermore, it may be composed of a single metal nanoparticle or a mixture of two or more metal nanoparticles.
  • the particle size of the metal nanoparticles is not particularly limited, and is selected from the range of, for example, 1 to 200 nm according to the purpose of use.
  • the dispersing agent of the present embodiment can provide an excellent dispersing effect even for metal nanoparticles having a small particle diameter, for example, 150 nm or less, particularly 100 nm or less, which cannot be expected with a known dispersing agent.
  • metal nanoparticles having a particle diameter of 150 nm or less are preferable, and metal nanoparticles having a particle diameter of 100 nm or less are more preferable.
  • the average particle diameter of the metal nanoparticles is preferably in the range of 10 to 150 nm, more preferably in the range of 20 to 120 nm.
  • the application method of the dispersant is not particularly limited.
  • a dispersing machine such as a high-pressure homogenizer
  • the tartaric acid derivative represented by the general formula (I) is solid (powder) at room temperature, it may be mixed with the metal nanoparticles as it is, or mixed with the metal nanoparticles in a state of being dissolved in an arbitrary solvent. Also good.
  • the amount of the dispersant used in the present embodiment is preferably in the range of 0.1 to 40 parts by mass with respect to 100 parts by mass of the metal nanoparticles, and preferably in the range of 1 to 30 parts by mass. The inside is more preferable. If the amount of the dispersant used relative to 100 parts by mass of the metal nanoparticles is less than 0.1 parts by mass, the dispersion effect tends to be insufficient, and if it exceeds 40 parts by mass, aggregates due to the residue of the dispersant tend to be generated. There is.
  • the product may be affected by the dispersant remaining in the metal nanoparticles.
  • the amount of the dispersant used is excessive, the volume change during firing in the production process will occur. It may become large and cause peeling or film breakage.
  • the washing can be performed using, for example, an alcohol solvent such as isopropanol.
  • the tartaric acid derivative represented by the general formula (I) has an excellent dispersing action on the metal nanoparticles is not yet clear, but the metal nanoparticles and the tartaric acid derivative represented by the general formula (I) It is presumed that some kind of interaction has occurred between them.
  • the tartaric acid derivative represented by the general formula (I) has two ester structures derived from a carboxylic acid in the molecule and two bulky or hydrophobic aromatic rings respectively involved in the formation of these ester structures. have. These ester structures-aromatic rings may be involved in the dispersion action.
  • interaction between the metal nanoparticles is caused by two ester structures-aromatic rings, and the presence of the tartaric acid derivative in the vicinity of the metal nanoparticles results in the electrical properties of the surface of the metal nanoparticles. It is considered that the agglomeration between the metal nanoparticles is suppressed by steric hindrance, or dispersibility is imparted by affinity with the solvent.
  • an ionic bond, a covalent bond, an electrostatic bond, a coordinate bond, a hydrogen bond, and the like can be considered.
  • the dispersant according to this embodiment By using the dispersant according to this embodiment, aggregation of fine metal nanoparticles having a particle size of 150 nm or less is suppressed, and aggregation of metal nanoparticles having a sharp particle size distribution in which single particles are dispersed. Can be obtained. Further, since the dispersant according to the present embodiment has a strong aggregation suppressing action, an excellent dispersion effect can be expected even in a small amount. Furthermore, by removing the excess dispersant, an effect of reducing the volatile matter generated in the baking process or the like can be obtained. As described above, the metal nanoparticles having few aggregated particles and having a sharp particle size distribution can be suitably used as an industrial material such as an internal electrode material of a multilayer ceramic capacitor.
  • the dispersible metal nanoparticle composition of the present invention contains a dispersant and metal nanoparticles.
  • the dispersant and the metal nanoparticles those described above are used.
  • the dispersible metal nanoparticle composition of the present invention may contain a solvent as an optional component.
  • the solvent is preferably an organic solvent from the viewpoint that it is difficult to change the state of the oxide or hydroxide film present on the surface of the metal nanoparticles, for example, an ether-based organic solvent having 4 to 30 carbon atoms, a carbon number of 7 A saturated or unsaturated hydrocarbon organic solvent having ⁇ 30, an alcohol solvent having 3 to 18 carbon atoms, or the like can be used.
  • the dispersant present in the dispersible metal nanoparticle composition of the present invention is more preferably an organic solvent in which the dispersant can be easily dissolved because it can easily exert its effect by being dissolved in the solvent.
  • the primary amine used for the liquid phase synthesis of the metal nanoparticles can be used as a solvent as it is.
  • the dispersant and the metal nanoparticle may form a composite.
  • the composite is a metal nanoparticle due to the interaction between the functional group of the tartaric acid derivative represented by the general formula (I) and the surface of the metal nanoparticle or a functional group (for example, hydroxyl group) present on the surface.
  • a functional group for example, hydroxyl group
  • the preparation of the dispersible metal nanoparticle composition is not particularly limited, and the dispersant and the metal nanoparticles may be mixed, and if necessary, kneading, stirring, or the like may be performed.
  • the application of the dispersant to the metal nanoparticles can be performed according to, for example, the above a) to c).
  • the content of the dispersant in the dispersible metal nanoparticle composition of the present embodiment is preferably in the range of 0.1 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the metal nanoparticles. More preferably within the range of not less than 30 parts and not more than 30 parts by mass.
  • the content of the dispersing agent with respect to 100 parts by mass of the metal nanoparticles is less than 0.1 parts by mass, the dispersibility tends to decrease, and when it exceeds 40 parts by mass, aggregation tends to occur.
  • the metal nanoparticles to which the dispersant of the present invention is applied or the metal nanoparticles contained in the dispersible metal nanoparticle composition of the present invention are not particularly limited as long as they are nanoparticles of the above-described metal species.
  • the particle size distribution is narrow with a particle size of 150 nm or less [for example, the coefficient of variation of particle size (CV value; standard deviation / average particle size) is 0.2 or less]
  • Metal nanoparticles are preferred. Although it is generally difficult to produce metal nanoparticles having such a particle size distribution, they can be produced by microwave irradiation in a liquid phase.
  • a manufacturing method by microwave irradiation in a liquid phase will be described. Further, in order to sufficiently exert the effect of the dispersant, it is preferable that a functional group such as a hydroxyl group is present on the surface of the metal nanoparticle, but the following is also easy to obtain such a metal nanoparticle.
  • the production method by microwave irradiation in the liquid phase described is suitable.
  • Nickel nanoparticles are produced in the following steps A and B; A) a complexing reaction liquid production step for obtaining a complexing reaction liquid by heating a mixture containing nickel carboxylate and a primary amine to a temperature in the range of 100 ° C. to 165 ° C .; as well as, B) Metal nickel nanoparticle slurry generation step of heating the complexing reaction liquid to a temperature of 170 ° C. or higher by microwave irradiation to reduce nickel ions in the complexing reaction liquid to obtain a metal nickel nanoparticle slurry. , It can prepare by the liquid phase method by microwave irradiation containing.
  • Nickel nanoparticles produced by microwave irradiation in the liquid phase contain, for example, oxygen atoms in the range of 0.5 to 5.0% by mass and carbon atoms in the range of 0.1 to 5.0% by mass. It is preferable to contain within. These oxygen atoms and carbon atoms are attached to the surface of the nickel nanoparticles as hydroxides or organic substances in the process of synthesizing the nickel nanoparticles by a liquid phase reaction.
  • the “nickel nanoparticle” may contain nickel element in an amount of 50% by weight or more, and may be a nickel alloy nanoparticle containing a metal other than nickel. In this case, examples of metals other than nickel include copper and cobalt.
  • Nickel carboxylate (nickel salt of carboxylic acid) is not limited to the type of carboxylic acid.
  • the carboxyl group may be a monocarboxylic acid having one carboxyl group, or a carboxylic acid having two or more carboxyl groups. It may be.
  • acyclic carboxylic acid may be sufficient and cyclic carboxylic acid may be sufficient.
  • nickel carboxylate nickel acyclic monocarboxylate can be suitably used, and among nickel acyclic monocarboxylate, nickel formate, nickel acetate, nickel propionate, nickel oxalate, benzoic acid It is more preferable to use nickel or the like. By using these nickel acyclic monocarboxylates, the resulting nickel nanoparticles are less likely to have a variation in shape and are easily formed as a uniform shape.
  • the nickel carboxylate may be an anhydride or a hydrate.
  • the primary amine is preferable because it can form a complex with nickel ions and effectively exhibits a reducing ability for nickel complexes (or nickel ions).
  • a secondary amine has a larger steric hindrance and a lower reducing ability than a primary amine, and thus may hinder good formation of a nickel complex.
  • the tertiary amine does not have the ability to reduce nickel ions, it is necessary to newly add a reducing agent.
  • these may be used together in the range which does not have trouble in the shape of the nickel nanoparticle to produce
  • the primary amine is not particularly limited as long as it can form a complex with nickel ions, and can be a solid or liquid at room temperature.
  • room temperature means 20 ° C. ⁇ 15 ° C.
  • the primary amine that is liquid at room temperature also functions as an organic solvent for forming the nickel complex.
  • it is a primary amine solid at normal temperature, there is no particular problem as long as it is liquid by heating at 100 ° C. or higher, or can be dissolved using an organic solvent.
  • the primary amine may be an aromatic primary amine, but an aliphatic primary amine is preferred from the viewpoint of easy nickel complex formation in the reaction solution.
  • Aliphatic primary amines can control the particle size of the produced nanoparticles, for example, by adjusting the length of the carbon chain, and in particular, produce nanoparticles having an average particle size in the range of 20 nm to 100 nm. This is advantageous.
  • the aliphatic primary amine is preferably selected from those having about 6 to 20 carbon atoms. The larger the carbon number, the smaller the particle size of the resulting nanoparticles.
  • amines examples include octylamine, hexadecylamine, dodecylamine, tetradecylamine, stearylamine, oleylamine, myristylamine, laurylamine and the like.
  • oleylamine exists in a liquid state under the temperature conditions in the nanoparticle production process, so that the reaction can proceed efficiently in a homogeneous solution.
  • the primary amine functions as a surface modifier during the production of the nanoparticles, secondary aggregation can be suppressed even after removal of the primary amine.
  • the primary amine is preferably a liquid at room temperature from the viewpoint of ease of processing operation in the washing step for separating the solid component of the produced nanoparticles from the solvent or the unreacted primary amine after the reduction reaction.
  • the primary amine preferably has a boiling point higher than the reduction temperature from the viewpoint of ease of reaction control when the nickel complex is reduced to obtain metallic nickel nanoparticles. That is, the aliphatic primary amine preferably has a boiling point of 180 ° C. or higher, more preferably 200 ° C. or higher, and preferably has 9 or more carbon atoms.
  • the boiling point of aliphatic amine [C 9 H 21 N (nonylamine)] having 9 carbon atoms is 201 ° C.
  • the amount of primary amine is preferably 2 mol or more, more preferably 2.2 mol or more, and more preferably 4 mol or more with respect to 1 mol of nickel.
  • an organic solvent different from the primary amine may be newly added in order to allow the reaction in the homogeneous solution to proceed more efficiently.
  • the organic solvent may be mixed simultaneously with the nickel carboxylate and the primary amine.
  • the organic solvent is added after first mixing the nickel carboxylate and the primary amine to form a complex, It is more preferable because it efficiently coordinates to a nickel atom.
  • the organic solvent that can be used is not particularly limited as long as it does not inhibit the complex formation between the primary amine and the nickel ion. For example, the organic solvent having 4 to 30 carbon atoms, the organic solvent having 7 to 30 carbon atoms, and the like.
  • a saturated or unsaturated hydrocarbon organic solvent, an alcohol organic solvent having 8 to 18 carbon atoms, or the like can be used. Further, from the viewpoint of enabling use even under heating conditions by microwave irradiation, it is preferable to select an organic solvent having a boiling point of 170 ° C. or higher, more preferably in the range of 200 to 300 ° C. It is better to choose one. Specific examples of such an organic solvent include tetraethylene glycol and n-octyl ether.
  • a divalent nickel ion is known as a ligand-substituted active species, and the ligand of the complex to be formed may easily change in complex formation by ligand exchange depending on temperature and concentration.
  • a carboxylate ion R 1 COO ⁇ , R 2 COO ⁇
  • a carboxylate ion R 1 COO ⁇ , R 2 COO ⁇
  • b monodentate coordination
  • the location needs to be coordinated by a primary amine.
  • this complex formation reaction can proceed even at room temperature, the reaction is carried out by heating to a temperature within the range of 100 ° C. to 165 ° C. in order to perform a sufficient and more efficient complex formation reaction.
  • This heating is particularly advantageous when nickel carboxylate hydrate such as nickel formate dihydrate or nickel acetate tetrahydrate is used as nickel carboxylate.
  • the heating temperature is preferably a temperature exceeding 100 ° C., more preferably a temperature of 105 ° C. or more, so that the ligand substitution reaction between the coordinating water coordinated with nickel carboxylate and the primary amine is efficient.
  • the water molecule as the complex ligand can be dissociated, and the water can be discharged out of the system, so that the complex with the amine can be efficiently formed.
  • nickel formate dihydrate has a complex structure in which two coordination waters and two formate ions as bidentate ligands exist at room temperature.
  • the heat treatment in the complex formation reaction between nickel carboxylate and primary amine is surely separated from the subsequent heat reduction process by microwave irradiation of the nickel complex (or nickel ion) to complete the complex formation reaction.
  • the temperature is set to the upper limit temperature or lower, preferably 160 ° C. or lower, more preferably 150 ° C. or lower.
  • the heating time can be appropriately determined according to the heating temperature and the content of each raw material, but is preferably 10 minutes or more from the viewpoint of completing the complex formation reaction. There is no upper limit on the heating time, but heat treatment for a long time is useless from the viewpoint of saving energy consumption and process time.
  • the heating method is not particularly limited, and may be heating by a heat medium such as an oil bath or heating by microwave irradiation.
  • the complex formation reaction between nickel carboxylate and primary amine can be confirmed by a change in the color of the solution when a solution obtained by mixing nickel carboxylate and primary amine in an organic solvent is heated. .
  • this complex formation reaction is carried out by measuring the absorption maximum wavelength of the absorption spectrum observed in the wavelength region of 300 nm to 750 nm using, for example, an ultraviolet / visible absorption spectrum measuring apparatus, and measuring the maximum absorption wavelength of the raw material (for example, nickel formate). In dihydrate, the maximum absorption wavelength is 710 nm, and in nickel acetate tetrahydrate, the maximum absorption wavelength is 710 nm.)
  • the shift of the complexing reaction solution (the maximum absorption wavelength shifts to 600 nm) is observed. Can be confirmed.
  • the resulting reaction solution is heated by microwave irradiation to reduce the nickel ions of the nickel complex as described below.
  • the carboxylate ions coordinated to the metal are decomposed, and finally metal nickel nanoparticles containing nickel having an oxidation number of 0 are generated.
  • nickel carboxylate is hardly soluble under conditions other than using water as a solvent, and a solution containing nickel carboxylate needs to be a homogeneous reaction solution as a pre-stage of the heat reduction reaction by microwave irradiation.
  • the primary amine used in the present embodiment is liquid under the operating temperature conditions, and is considered to be liquefied by coordination with nickel ions to form a homogeneous reaction solution.
  • the complexing reaction solution obtained by the complexation reaction between nickel carboxylate and primary amine is heated to a temperature of 170 ° C. or higher by microwave irradiation to reduce nickel ions in the complexing reaction solution.
  • the temperature for heating by microwave irradiation is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, from the viewpoint of suppressing variation in the shape of the obtained nanoparticles.
  • the upper limit of the heating temperature is not particularly limited, but is preferably set to 270 ° C. or less, for example, from the viewpoint of efficiently performing the treatment.
  • the use wavelength of a microwave is not specifically limited, For example, it is 2.45 GHz.
  • the heating temperature can be appropriately adjusted depending on, for example, the type of nickel carboxylate or the use of an additive that promotes the nucleation of metallic nickel nanoparticles.
  • a nickel complex is uniformly and sufficiently produced in the complexing reaction solution producing step (step in which nickel complex is produced) in step A, and this step B
  • the step of heating by microwave irradiation it is necessary to simultaneously generate and grow nickel (zero-valent) nuclei generated by reduction of the nickel complex (or nickel ion).
  • the heating temperature in the complexing reaction liquid generation step within the above specific range and ensuring that it is lower than the heating temperature by the microwave in the nanoparticle slurry generation step, the particle size and shape are adjusted. Particles are easily generated.
  • the heating temperature in the nanoparticle slurry generation step is too high, the reduction reaction rate to nickel (zero valence) is slowed and the generation of nuclei is reduced, so that not only the particles are enlarged, but also from the viewpoint of the yield of nanoparticles. Is also not preferred.
  • the nickel metal nanoparticles slurry obtained by heating by microwave irradiation is, for example, statically separated, and after removing the supernatant, washed with an appropriate solvent and dried to obtain nickel nanoparticles. .
  • the organic solvent described above may be added as necessary.
  • the primary amine used for the complex formation reaction is preferably used as it is as the organic solvent.
  • nickel nanoparticles having a hydroxyl group on the surface and an average particle diameter of 150 nm or less can be prepared. Note that not only nickel nanoparticles but also other metal nanoparticles can be produced according to the above method.
  • the average particle size was measured by taking a photograph of the sample with an SEM (scanning electron microscope), randomly extracting 200 samples from the sample, obtaining each particle size, and calculating the average particle size.
  • Nickel nanoparticles were obtained.
  • the average particle diameter of the nickel nanoparticles thus obtained was 100 nm.
  • the nickel nanoparticles were C; 0.9, N; ⁇ 0.1, O; 1.4 (unit: mass%).
  • Example 1-1 10 g of the slurry solution 1 prepared in Reference Example 1 was fractionated, 0.2 g of di-p-toluoyl-L-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and the particle size distribution was measured. went. The results are shown in Table 1.
  • Example 1-2 10 g of the slurry solution 1 prepared in Reference Example 1 was fractionated, 0.2 g of dibenzoyl-D-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and the particle size distribution was measured. The results are shown in Table 1.
  • Example 1-3 10 g of the slurry solution 1 prepared in Reference Example 1 was fractionated, 0.2 g of di-p-anisoyl-D-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and particle size distribution measurement Went. The results are shown in Table 1.
  • Example 2-1 Take 10 g of the slurry solution 2 prepared in Reference Example 2, add 0.2 g of di-p-toluoyl-L-tartaric acid, stir for 15 minutes, wash with isopropanol, and measure the particle size distribution. went. The results are shown in Table 2.
  • Example 2-2 Take 10 g of the slurry solution 2 prepared in Reference Example 2, add 0.2 g of di-p-toluoyl-D-tartaric acid, stir for 15 minutes, wash with isopropanol, and measure the particle size distribution. went. The results are shown in Table 2.
  • Example 2-3 10 g of the slurry solution 2 prepared in Reference Example 2 was fractionated, 0.2 g of dibenzoyl-L-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and the particle size distribution was measured. The results are shown in Table 2.
  • Example 2-4 Take 10 g of the slurry solution 2 prepared in Reference Example 2, add 0.2 g of di-p-anisoyl-L-tartaric acid, stir for 15 minutes, wash with isopropanol, and measure the particle size distribution. went. The results are shown in Table 2.
  • Example 3-1 Take 10 g of slurry solution 3 prepared in Reference Example 3, add 0.2 g of di-p-toluoyl-L-tartaric acid, stir for 15 minutes, wash with isopropanol, and measure the particle size distribution. went. The results are shown in Table 3.
  • Example 3-2 10 g of the slurry solution 3 prepared in Reference Example 3 was fractionated, 0.2 g of di-p-toluoyl-D-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and particle size distribution measurement Went. The results are shown in Table 3.
  • Example 3-3 10 g of the slurry solution 3 prepared in Reference Example 3 was fractionated, 0.2 g of di-o-toluoyl-L-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and particle size distribution measurement Went. The results are shown in Table 3.
  • examples of the volume distribution D90 [particle diameter at which the cumulative particle size distribution (volume basis) from the small particle diameter side becomes 90%] and D99 [particle diameter at 99% from the small particle diameter side], which are rough coarse aggregated particles, are given as examples As compared with the comparative example, it was confirmed that the particle size was extremely small, the aggregated particles were few, the particle size distribution was sharp, and the dispersibility was good.

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  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

Dispersant comprenant un dérivé d'acide tartrique représenté par la formule générale (I) [les groupes R1 et R2 représentant indépendamment un groupe phényle qui peut être substitué]. Dans la formule générale (I), le groupe phényle qui peut être substitué est de préférence un groupe phényle, un groupe tolyle, ou un groupe anisoyle. Le dispersant peut être utilisé de préférence pour la dispersion de nanoparticules métalliques. Une composition de nanoparticules métalliques susceptibles de dispersion comprenant des nanoparticules métalliques et le dispersant est également décrite.
PCT/JP2012/071395 2011-08-26 2012-08-24 Dispersant, et composition de nanoparticules métalliques susceptibles de dispersion WO2013031670A1 (fr)

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JP2014162966A (ja) * 2013-02-26 2014-09-08 Nippon Steel & Sumikin Chemical Co Ltd 金属微粒子組成物、接合材、電子部品、接合層の形成方法、導体層の形成方法及びインク組成物
JP2014188561A (ja) * 2013-03-28 2014-10-06 Nippon Steel & Sumikin Chemical Co Ltd 接合方法
CN114905049A (zh) * 2022-05-11 2022-08-16 江南大学 一种手性钴超粒子及其制备方法

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
JP2014162966A (ja) * 2013-02-26 2014-09-08 Nippon Steel & Sumikin Chemical Co Ltd 金属微粒子組成物、接合材、電子部品、接合層の形成方法、導体層の形成方法及びインク組成物
JP2014188561A (ja) * 2013-03-28 2014-10-06 Nippon Steel & Sumikin Chemical Co Ltd 接合方法
CN114905049A (zh) * 2022-05-11 2022-08-16 江南大学 一种手性钴超粒子及其制备方法
CN114905049B (zh) * 2022-05-11 2023-06-02 江南大学 一种手性钴超粒子及其制备方法

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