WO2015122430A1 - Method for producing metal nanoparticles - Google Patents

Method for producing metal nanoparticles Download PDF

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Publication number
WO2015122430A1
WO2015122430A1 PCT/JP2015/053751 JP2015053751W WO2015122430A1 WO 2015122430 A1 WO2015122430 A1 WO 2015122430A1 JP 2015053751 W JP2015053751 W JP 2015053751W WO 2015122430 A1 WO2015122430 A1 WO 2015122430A1
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metal
mol
compound
production method
composition
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PCT/JP2015/053751
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French (fr)
Japanese (ja)
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謙輔 川村
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ダイソー株式会社
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Application filed by ダイソー株式会社 filed Critical ダイソー株式会社
Priority to KR1020167017560A priority Critical patent/KR102260398B1/en
Priority to JP2015562841A priority patent/JP6414085B2/en
Priority to CN201580008570.8A priority patent/CN105992663B/en
Publication of WO2015122430A1 publication Critical patent/WO2015122430A1/en

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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
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • 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
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

  • the present invention relates to a method for producing metal nanoparticles.
  • printed electronics which is a new circuit formation (patterning) method that replaces conventional plating methods and vapor deposition-photolithography methods, and directly forms circuits by printing, has attracted attention as the next-generation industrial base. ing.
  • This technology forms a desired circuit pattern by printing a conductive paste or conductive ink on a substrate, from basic circuit components such as thin film transistors, resistors, inductors, capacitors, batteries, and displays.
  • Sensors, RFID (Radio Frequency Identification), and many application products such as solar cells can be widely applied.
  • the adoption of printed electronics is expected to dramatically simplify the manufacturing process of electronics-related products, reduce time, and achieve further resource and energy savings at the same time.
  • nano-particles mean those with an average particle diameter of 1 nm to 100 nm.
  • the melting temperature is significantly lower than that of bulk metal due to the nano-size effect due to the increase in surface energy in addition to its high electrical conductivity, thus lowering the processing temperature during the circuit formation process.
  • a material having a smaller average particle diameter has been aimed at.
  • nanoparticles with a small average particle size become unstable and easily aggregate due to an increase in surface energy. Therefore, when used as a material such as various conductive inks or conductive pastes during the production of nanoparticles. Problems such as precipitation and solid-liquid separation occurred.
  • various studies have been made on techniques for coating nanoparticles with various protective layers. As a result, it has become possible to produce and use extremely minute metal nanoparticles having a size of 10 nm or less.
  • Patent Document 1 describes a method of preparing metal nanoparticle having a mean particle diameter of 3 nm to 20 nm by a reduction reaction in a liquid phase using silver oxide as a raw material as a method for producing metal nanoparticle.
  • Patent Document 2 silver having an average particle diameter D TEM : 3 to 20 nm or an X-ray crystal particle diameter D X : 1 to 20 nm coated with a film containing an unsaturated bond and a primary amine having a molecular weight of 200 to 400 is disclosed.
  • an amine mixed solution containing an alkylamine having 6 or more carbon atoms and an alkylamine having 5 or less carbon atoms and a metal compound containing a metal atom are mixed to contain the metal compound and the amine.
  • a method for producing coated metal fine particles comprising a first step of producing a complex compound and a second step of decomposing the complex compound by heating to produce metal fine particles, It is disclosed that the obtained silver fine particles have an average particle diameter of 30 nm or less.
  • the average particle diameter of the coated metal fine particles obtained in the examples measured by a transmission electron microscope (TEM) and a dynamic light scattering (DLS) particle diameter measuring apparatus is 20 nm or less.
  • the surface of the metal nanoparticles is organic molecules or the like in order to uniformly disperse highly cohesive metal nanoparticles in the conductive ink. It is necessary to be coated with.
  • the specific surface area of the metal nanoparticle increases as the average particle diameter of the metal nanoparticle decreases, the amount of organic molecules covering the surface of the metal nanoparticle increases. Therefore, when a circuit pattern is formed using the metal nanoparticles, organic molecules remain in the circuit, and the original conductivity of the metal nanoparticles cannot be obtained.
  • Patent Document 4 discloses metal colloidal particles containing metal nanoparticles (A) and a dispersant (B), wherein the metal nanoparticles ( A) is a metal in a solvent in the presence of metal colloidal particles containing metal nanoparticles having a number average particle size of 50 nm or less and a particle size of 100 to 200 nm, and a dispersant (B) and / or a precursor thereof.
  • a method for producing metal colloidal particles comprising the steps of reducing a compound to produce metal colloidal particles, producing aggregates of metal colloidal particles as precipitates, and separating and recovering the aggregates produced in this step Is described.
  • Patent Document 4 since the manufacturing method described in Patent Document 4 uses a polymer dispersant, it is necessary to remove the polymer dispersant by heat treatment at about 300 ° C. in order to obtain conductivity. Become. Therefore, the use for a film base material is restricted.
  • An object of the present invention is to provide a production method capable of efficiently producing metal nanoparticles having an average particle diameter of about 20 nm or more and 200 nm or less, wherein a circuit pattern formed using the metal nanoparticles has high electrical conductivity. It is an issue to provide.
  • Item 1 It is a manufacturing method of the metal nanoparticle which makes the composition containing a metal compound (a) and an amine compound (b) react, Comprising: Content of the amine compound (b) in a composition is contained in a metal compound (a) The method is characterized by being in the range of more than 0 mol and not more than 1 mol with respect to 1 mol of the metal atom.
  • Item 2. Item 2. The method according to Item 1, wherein the composition further comprises an organic solvent (c) that dissolves 1 g / L or more in water at 20 ° C.
  • Item 3. Item 3.
  • a conductive ink composition or a conductive paste containing metal nanoparticles obtained by the production method according to any one of Items 1 to 9.
  • Item 12. A circuit wiring or electrode formed using the conductive ink composition according to Item 11, or a conductive paste.
  • the metal compound (a) and the amine compound (b) are contained, and the amine compound (b) exceeds about 0 mol and 1 mol with respect to 1 mol of the metal atom contained in the metal compound (a).
  • the amine compound (b) exceeds about 0 mol and 1 mol with respect to 1 mol of the metal atom contained in the metal compound (a).
  • the metal nanoparticles obtained by the method of the present invention have a small amount of remaining organic molecules covering the surface, heat treatment can be performed in a short time or at a relatively low temperature by using a conductive ink or paste containing the metal nanoparticles.
  • a circuit pattern or an electrode exhibiting high electrical conductivity can be obtained only by the above. Therefore, the present invention can provide an extremely excellent printed electronics material.
  • 4 is a SEM (scanning electron microscope) photograph of silver nanoparticles obtained in Example 4.
  • 4 is a SEM (scanning electron microscope) photograph of silver nanoparticles obtained in Example 5.
  • 2 is a SEM (scanning electron microscope) photograph of silver nanoparticles obtained in Comparative Example 1.
  • 4 is a SEM (scanning electron microscope) photograph of silver nanoparticles obtained in Comparative Example 2.
  • composition used in the method for producing metal nanoparticles contains a metal compound (a) and an amine compound (b), and the content of the amine compound (b) in the composition is: It is characterized by being in the range of more than about 0 mol and 1 mol or less with respect to 1 mol of the metal atom contained in the metal compound (a).
  • metal nanoparticles having an average particle size of about 20 nm to 200 nm for example, about 20 nm to 150 nm, particularly about 20 nm to 100 nm
  • the average particle diameter of the metal nanoparticle in the present invention is an average value (D SEM ) of long sides of 20 particles measured from an image of a scanning electron microscope (SEM).
  • D SEM scanning electron microscope
  • metal nanoparticles having a DSEM of about 20 nm to 200 nm are preferable.
  • the metal nanoparticles in the above average particle diameter range are advantageous for producing a conductive ink or a conductive paste having good conductivity.
  • the composition used in the production method of the present invention may further contain an organic solvent (c).
  • an organic solvent (c) When the composition contains the organic solvent (c), it becomes easy to uniformly mix the metal compound (a) and the amine compound (b) in the composition, the thermal decomposition reaction proceeds efficiently, and efficiently. Metal nanoparticles are generated.
  • the metal nanoparticles obtained in the present invention are coated with a protective layer on the surface of the metal nanoparticles in order to prevent aggregation in the conductive ink or conductive paste and to disperse them well in a desired solvent. It is necessary. Therefore, the composition used for the production method of the present invention contains an amine compound (b) that can be a protective layer together with the metal compound (a).
  • composition used in the production method of the present invention can contain an additive for fine metal particles applied to printed electronics as required, as long as the effect of the present invention is not affected.
  • Specific additives include fatty acid (d), viscosity adjusting agent, conductive additive, anti-choking agent, antioxidant, pH adjusting agent, anti-drying agent, adhesion promoter, antiseptic, antifoaming agent, leveling agent. And surfactants.
  • Metal compound (a) As the metal compound (a) used in the production method of the present invention, an organic metal salt such as a metal carboxylate; an inorganic metal salt such as a metal sulfonate, thiol salt, chloride, nitrate, or carbonate Can be illustrated. Among them, organic metal salts and carbonates are preferable, and organic metal salts are more preferable in that it is easy to remove counterion-derived substances after the formation of metal nanoparticles, and formic acid, acetic acid, oxalic acid, malonic acid are particularly preferable.
  • Carboxylic acid salts such as benzoic acid and phthalic acid are more preferred, and oxalates are even more preferred from the viewpoint of easiness of thermal decomposition.
  • a metal compound can be used individually or in combination of 2 or more types.
  • a commercial item can be purchased and used for a metal compound (a).
  • Examples of the metal species of the metal compound (a) include gold, silver, copper, platinum, palladium, nickel, and aluminum. Of these, gold, silver, and platinum are preferable in terms of conductivity and oxidation resistance, and silver is more preferable in terms of cost and low-temperature sinterability. Copper, nickel, and aluminum are also preferable.
  • gold formate, silver formate, copper formate, platinum formate, palladium formate, nickel formate, aluminum formate gold acetate, silver acetate, copper acetate, platinum acetate, palladium acetate, nickel acetate, acetic acid
  • gold oxalate, silver oxalate, copper oxalate, platinum oxalate, palladium oxalate, nickel oxalate, aluminum oxalate gold malonate, silver malonate, copper malonate, platinum malonate, palladium malonate, nickel malonate, aluminum malonate
  • Examples thereof include gold phthalate, silver phthalate, copper phthalate, platinum phthalate, palladium phthalate, nickel phthalate, and aluminum phthalate.
  • the content of the metal compound (a) in the composition is preferably 1% by weight or more, more preferably 10% by weight or more, and still more preferably 20% by weight or more based on the entire composition. Moreover, 95 weight% or less is preferable, 80 weight% or less is more preferable, and 70 weight% or less is still more preferable.
  • the content of the metal compound (a) in the composition is about 1 to 95% by weight, about 1 to 80% by weight, about 1 to 70% by weight, about 10 to 95% by weight, about 10 to 80% by weight, Examples include about 10 to 70% by weight, about 20 to 95% by weight, about 20 to 80% by weight, and about 20 to 70% by weight. If it is in the said range, the effect of this invention can fully be acquired.
  • Amine compound (b) The amine compound (b) used in the production method of the present invention has an ability to bind to the metal compound (a), and can form a protective layer on the surface of the metal nanoparticle when the metal nanoparticle is generated. Anything can be used without limitation.
  • two primary amine compounds (b-1) which are compounds in which one is substituted with a linear, branched, or cyclic hydrocarbon group, are similarly substituted.
  • Examples include the secondary amine compound (b-2) and the tertiary amine compound (b-3) in which three are similarly substituted.
  • the ability to bind to the metal compound (a) is high, and when a conductive ink or conductive paste using the obtained metal nanoparticles is applied on a substrate, the temperature is relatively low (for example, 120 ° C. or lower).
  • the primary amine compound (b-1) is preferable in that it is easily detached from the surface of the metal nanoparticle by the heat treatment.
  • Examples of the primary amine compound (b-1) include ethylamine, n-propylamine, isopropylamine, 1,2-dimethylpropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, isoamylamine, tert -Amylamine, 3-pentylamine, n-amylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-octylamine, tert-octylamine, 2-ethylhexylamine, n-nonylamine, n-aminodecane, n-aminoundecane, n-dodecylamine, n-tridecylamine, 2-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexade
  • cyclopropylamine, cyclobutylamine, cyclopropylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine that are alicyclic amines, aniline that is an aromatic amine, and the like can also be exemplified.
  • ether amines such as 3-isopropoxypropylamine and isobutoxypropylamine can also be exemplified.
  • tertiary amine compound (b-3) triethylamine, tributylamine, trihexylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dilaurylmonomethyl An amine etc. can be illustrated.
  • a diamine compound (b-4) having two amino groups in one compound can also be used.
  • the diamine compound (b-4) include ethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, 1,3-propanediamine, , 2-Dimethyl-1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N'-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propane Diamine, N, N′-diethyl-1,3-propanediamine, 1,4-butanediamine, N, N-dimethyl-1,4-butanediamine, N, N′-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N′-diethyl-1,4-but
  • a diamine compound in which one of the amines is a primary amine and the other is a tertiary amine is excellent in binding ability with the metal compound (a), and metal nanoparticles are formed. Moreover, it is preferable in that a protective layer can be easily formed on the surface of the metal nanoparticle.
  • diamine compounds in which one is a primary amine and the other is a tertiary amine include N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-propanediamine, and N, N.
  • An amine compound (b) can be used individually by 1 type or in combination of 2 or more types. Specifically, one or more of (b-1), (b-2), (b-3), and (b-4) can be used, in particular, only (b-1), Only (b-4) and a combination of (b-1) and (b-4) are preferred. Furthermore, 1 or more types can be used among each group of (b-1), (b-2), (b-3), (b-4).
  • the content of the amine compound (b) in the composition may be in the range of more than about 0 mol and 1 mol or less with respect to 1 mol of the metal atom contained in the metal compound (a).
  • the content of the amine compound (b) is preferably 0.1 mol or more, more preferably 0.2 mol or more, even more preferably 0.3 mol or more, with respect to 1 mol of the metal atom contained in the metal compound (a).
  • Preferably, 0.4 mol or more is even more preferable.
  • 0.9 mol or less is preferable with respect to 1 mol of substance amounts of the metal atom contained in a metal compound (a), and, as for content of an amine compound (b), 0.8 mol or less is more preferable.
  • the content of the amine compound (b) with respect to 1 mol of the metal atom contained in the metal compound (a) is more than about 0 mol and 1 mol or less, about 0.1 mol or more and 1 mol or less, about 0.2 mol.
  • the amine compound (b) contained in the composition used for production forms a circuit pattern (conductive film) by subjecting the conductive ink or conductive paste containing the obtained metal nanoparticles to heat treatment.
  • the substance amount (mol) of the amine compound (b) in the present invention is the primary amine compound (b-1) in which one, two, or three of the three hydrogen atoms of ammonia are substituted with a hydrocarbon group. ), Secondary amine compound (b-2), or tertiary amine compound (b-3), the primary amine, secondary amine, or secondary site that is coordinated to the metal compound (a) Calculation is based on the number of tertiary amines. That is, the number of moles of molecules is defined as a substance amount (mol).
  • the amount (mol) of the amine compound (b) is based on the number of primary amines and secondary amines in the diamine compound (b-4) having primary amines and / or secondary amines. And That is, the substance amount (mol) of a diamine compound having two primary amines or two secondary amines, or one primary amine and one secondary amine, is twice the number of moles of the molecule. .
  • the amount (mol) of the amine compound (b) is the number of primary amines or secondary amines in the case of a diamine compound in which one is a primary amine or secondary amine and the other is a tertiary amine. Is calculated based on That is, the number of moles of molecules is the amount of substance (mol).
  • the tertiary amine has a large steric hindrance and is difficult to coordinate with the metal compound (a), so that the primary amine or the secondary amine can be easily coordinated with the metal compound (a). This is because it is appropriate to use numbers as the basis.
  • Organic solvent (c) The organic solvent (c) is not limited thereto, but preferably dissolves in an amount of about 1 g / L or more in water at 20 ° C., more preferably dissolves in an amount of about 10 g / L or more.
  • An organic solvent having both an ether bond and a hydroxyl group in one compound (organic solvent) can be preferably used. This organic compound may have a bond other than an ether bond and a functional group other than a hydroxyl group.
  • organic solvent (c) examples include aromatic compounds such as benzene and benzonitrile, ketones such as acetone, acetylacetone, and methyl ethyl ketone, fatty acid esters such as ethyl acetate, butyl acetate, ethyl butyrate, and ethyl formate, diethyl ether, dipropyl Ethers such as ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-pentanediol, 1,5-pentane
  • 3-methoxy is low in that since it has a high boiling point, it is less likely to evaporate during the thermal decomposition reaction of the metal compound (a) and take heat away from the system, and each component can be well dispersed in the composition.
  • Alcohols having an alkoxy group such as 1-butanol, 3-methoxy-3-methyl-1-butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol mono Glycol ethers such as ethyl ether and triethylene glycol monoethyl ether are preferred.
  • the content of the organic solvent (c) in the composition is not particularly limited, but is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and 30 parts by weight with respect to 1 part by weight of the metal compound (a). Part or more is even more preferable. If it is this range, each component in a composition can be mixed uniformly. Moreover, 1000 weight part or less is preferable with respect to 1 weight part of metal compounds (a), and, as for content of the organic solvent (c) in a composition, 500 weight part or less is preferable and 300 weight part or less is preferable. Within this range, it is possible to avoid situations where the reaction solution becomes too dilute and the reaction becomes longer or the recovery cost increases.
  • the content of the organic solvent (c) in the composition is about 5-1000 parts by weight, about 5-500 parts by weight, about 5-300 parts by weight, about 10 parts by weight with respect to 1 part by weight of the metal compound (a). -1000 parts by weight, about 10-500 parts by weight, about 10-300 parts by weight, about 30-1000 parts by weight, about 30-500 parts by weight, and about 30-300 parts by weight.
  • Fatty acid (d) Fatty acid (d) may be further added to the composition used in the production method of the present invention as necessary. Since the fatty acid (d) binds strongly to the surface of the metal nanoparticles, it contributes to the improvement of the dispersibility of the metal nanoparticles in the conductive ink or conductive paste.
  • the fatty acid (d) is not particularly limited as long as it has an ability to bind to the metal compound (a) and functions as a protective layer on the surface of the metal nanoparticle when the metal nanoparticle is generated. be able to.
  • the fatty acid (d) may have 3 to 18 carbon atoms, and preferably has 4 to 18 carbon atoms.
  • Cyclic alkyl carboxylic acids such as cyclohexane carboxylic acid can also be used.
  • caproic acid 2-ethylhexylic acid, oleic acid, linoleic acid, and ⁇ -linolenic acid are preferred because of good dispersion stability in the reaction solution during the production of metal nanoparticles.
  • the fatty acid (d) can be used alone or in combination of two or more.
  • the content of the fatty acid (d) in the composition is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and further preferably 1 part by weight or more with respect to 1 part by weight of the metal compound (a). More preferred. If it is this range, the dispersibility improvement effect of a metal nanoparticle will be fully acquired.
  • the content of the fatty acid (d) in the composition is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, and still more preferably 8 parts by weight or less, relative to 1 part by weight of the metal compound (a). .
  • fatty acid (d) binds strongly to metal nanoparticles, and in a heat treatment usually performed when a conductive ink using metal nanoparticles or a conductive paste is applied on a substrate, Although it is hard to detach
  • the content of the fatty acid (d) with respect to 1 part by weight of the metal compound (a) is about 0.1 part by weight to 15 parts by weight, about 0.5 part by weight to 15 parts by weight, about 1 part by weight to 15 parts by weight.
  • Parts by weight about 0.1 to 10 parts by weight, about 0.5 to 10 parts by weight, about 1 to 10 parts by weight, about 0.1 to 8 parts by weight, about 0.5 parts by weight or more and 8 parts by weight or less, and about 1 part by weight or more and 8 parts by weight or less are included.
  • the molar ratio of the amine compound (a) to the fatty acid (d) is such that the amine compound (a): fatty acid (d) is in the range of about 90:10 to about 99.9: 0.1, and about 95: It is preferably in the range of 5 to about 99.9: 0.1, and preferably in the range of about 95: 5 to about 99.5: 0.5. If it is within the above range, it is a protective layer that can sufficiently improve the dispersibility of the metal nanoparticles, and when the conductive ink containing the metal nanoparticles or the conductive paste is applied on the substrate, the comparison is made. A protective layer that is easily detached from the surface of the metal nanoparticle can be formed by heat treatment at a low temperature.
  • metal nanoparticle having an average particle diameter of about 20 nm to 200 nm can be produced.
  • the production method of the present invention can include an adjustment process of the composition, but the composition prepared in advance can also be used.
  • the mixing method and mixing order of each component in the adjusting step are not particularly limited as long as each component is uniformly dispersed in the composition and becomes a mixed state.
  • Examples of mixing methods include mechanical stirrers, magnetic stirrers, vortex mixers, planetary mills, ball mills, three rolls, line mixers, planetary mixers, dissolvers, etc., and these methods can be used according to the scale and capacity of the production equipment. Can be selected as appropriate from the above.
  • Reaction Step By subjecting the composition described above to a thermal reaction (reaction step) in a reaction vessel, a thermal decomposition reaction of the metal compound (a) occurs, and metal nanoparticles are generated.
  • the reaction method is not particularly limited as long as it is a method usually performed in a method for producing metal nanoparticles used for printed electronics.
  • the composition may be introduced into a reaction vessel that has been heated in advance, or the composition may be heated after being introduced into the reaction vessel.
  • the reaction temperature of the pyrolysis reaction in the reaction step of the present invention may be a temperature at which the pyrolysis reaction proceeds and metal nanoparticles are generated, may be 50 ° C. or more, preferably 100 ° C. or more, and preferably 120 ° C. The above is more preferable. If it is this range, a metal nanoparticle will produce
  • the reaction temperature is about 50 ° C to 250 ° C, about 100 ° C to 250 ° C, about 120 ° C to 250 ° C, about 50 ° C to 240 ° C, about 100 ° C to 240 ° C, about 120 ° C to 240 ° C. Or less, about 50 to 230 ° C., about 100 to 230 ° C., about 120 to 230 ° C.
  • the reaction time may be appropriately selected according to the desired average particle size and the composition of the composition corresponding thereto. For example, it may be about 1 minute to 100 hours, and preferably about 1 minute to 10 hours.
  • purification process pyrolysis reaction is obtained as a mixture containing an unreacted raw material (an organic solvent when an organic solvent (c) is added).
  • the target metal nanoparticles can be obtained.
  • the purification method include a precipitation method using the specific gravity difference between the metal nanoparticles and the organic solvent, in addition to a solid-liquid separation method by a normal filter filtration.
  • a specific method of solid-liquid separation a method such as centrifugation, a cyclone method, or a decanter can be exemplified.
  • the mixture may be diluted with a low-boiling solvent such as acetone or methanol in order to adjust the viscosity of the mixture containing metal nanoparticles.
  • metal nanoparticles having a desired average particle size can be obtained by appropriately adjusting the reaction conditions and the composition of the composition used for the reaction.
  • the average particle size can be in the range of about 20 nm to 200 nm, in the range of about 20 nm to 150 nm, and in the range of about 20 nm to 100 nm.
  • the metal nanoparticles obtained by the production method of the present invention can be easily dispersed in various solvents when used in a conductive ink or conductive paste. Furthermore, since a circuit formed using metal nanoparticles obtained by the production method of the present invention exhibits a low volume resistance value, it can be used for various conductive materials.
  • Metal compound (a) a1 Silver oxalate ((COOAg) 2 )
  • the molar ratio of the amine compound (b) to 0.5 mol of silver oxalate (1 mol of silver atoms) was adjusted in the range of more than 0 mol and 1 mol or less.
  • Silver oxalate was synthesized by the method described in Patent Document 3 (Japanese Patent Application Laid-Open No. 2012-162767).
  • the liquid (b) liquid mixture was prepared and used for all the Examples and Comparative Examples.
  • the obtained metal nanoparticles and the conductive ink using the same were dark amber and the average particle size was 77.9 nm.
  • Example 2 was the same as Example 1 except that the organic solvent (c) was added. After the organic solvent (c) was added, the metal compound and the amine compound were more uniformly dispersed in the composition as compared with Example 1. The average particle diameter of the obtained metal nanoparticles was 23.5 nm.
  • the time from the start of heating to the start of the reaction was longer than that of Example 2 and Example 3, and was about 15 minutes.
  • the average particle diameter of the obtained metal nanoparticles was 53.7 nm.
  • Example 5 was the same as Example 2 except that the organic solvent (c) was changed to diethylene glycol monobutyl ether.
  • the composition was uniformly dispersed as in Examples 2-4. In addition, it took about 10 minutes from the start of heating to the start of the reaction.
  • the average particle diameter of the obtained metal nanoparticles was 28.8 nm.
  • the average particle diameter of the obtained metal nanoparticles was 16.4 nm, and metal nanoparticles having an average particle diameter of 20 nm or more were not obtained.
  • the average particle diameter of the obtained metal nanoparticles was 18.7 nm, and metal nanoparticles having an average particle diameter of 20 nm or more were not obtained.
  • the resistance value tends to be lower as the average particle size of the metal nanoparticles is larger regardless of the presence or absence of heat treatment. This is because the coating of the amine compound (b) remains on the surface of the metal nanoparticle because the temperature is low at room temperature and heat treatment at 70 ° C., and the metal nanoparticle having a large particle diameter, that is, a specific surface area is small. However, it is considered that the resistance value was lowered because the remaining amount of the amine compound was small.
  • the conductivity of the metal nanoparticles of each example of the present invention was almost equal to or higher than the conductivity of the metal nanoparticles of the comparative example having an average particle diameter of less than 20 nm.
  • the metal nanoparticles of each example of the present invention have a relatively large average particle diameter, the amount of the protective layer is relatively small, and accordingly, the heat treatment time of the conductive ink or paste containing the metal nanoparticles is increased. It can be shortened or the heat treatment temperature can be lowered. That is, the metal nanoparticles of the present invention can reduce the heat treatment temperature or time of the conductive ink or paste while maintaining the high conductivity of the metal nanoparticles having an average particle diameter of less than 20 nm.
  • the conductive ink prepared by using the metal nanoparticles obtained by the production method of the present invention exhibits high electrical conductivity by a short heat treatment, and thus is not limited by the heat resistance of the base material. It can be applied to various printing methods for a wide range of substrates such as polymer films. Specifically, it can be effectively used as a material for printed electronics used for electric circuit wiring and electrode formation. Furthermore, the metal nanoparticles obtained by the production method of the present invention can be effectively used in various fields such as conductive adhesives, electromagnetic wave absorbers, and light reflectors.

Abstract

This method is a method for producing metal nanoparticles, wherein a composition containing a metal compound (a) and an amine compound (b) is reacted. The content of the amine compound (b) in the composition is more than 0 mol but 1 mol or less relative to 1 mol of a metal atom contained in the metal compound (a). This method enables the achievement of metal nanoparticles which provide a conductive ink or paste for printed electronics, said conductive ink or paste leaving less residue after firing and developing high conductivity by a low-temperature treatment.

Description

金属ナノ微粒子の製造方法Method for producing metal nanoparticles
　本発明は、金属ナノ微粒子の製造方法に関するものである。 The present invention relates to a method for producing metal nanoparticles.
　近年、従来のめっき法や蒸着－フォトリソグラフィー法に代わる新たな回路形成（パターニング）方法であり、印刷によって直接回路を形成する技術である「プリンテッドエレクトロニクス」が、次世代の産業基盤として注目されている。この技術は、導電性ペースト、又は導電性インクを基板に印刷することにより、所望の回路パターンを形成するものであり、薄膜トランジスタ、抵抗、インダクター、コンデンサー等の基本的な回路部品から、電池、ディスプレイ、センサー、ＲＦＩＤ　(Ｒａｄｉｏ　Ｆｒｅｑｕｅｎｃｙ　Ｉｄｅｎｔｉｆｉｃａｔｉｏｎ)、太陽電池等の多数の応用製品まで広く応用が可能である。プリンテッドエレクトロニクスの採用により、エレクトロニクス関連製品の製造工程が、劇的に簡便になり、時間が短縮され、更なる省資源及び省エネルギー化も同時に達成できることが期待されている。 In recent years, “printed electronics”, which is a new circuit formation (patterning) method that replaces conventional plating methods and vapor deposition-photolithography methods, and directly forms circuits by printing, has attracted attention as the next-generation industrial base. ing. This technology forms a desired circuit pattern by printing a conductive paste or conductive ink on a substrate, from basic circuit components such as thin film transistors, resistors, inductors, capacitors, batteries, and displays. , Sensors, RFID (Radio Frequency Identification), and many application products such as solar cells can be widely applied. The adoption of printed electronics is expected to dramatically simplify the manufacturing process of electronics-related products, reduce time, and achieve further resource and energy savings at the same time.
　プリンテッドエレクトロニクスには、ガラス基板及びポリマーフィルムの何れも用いることができるが、フィルム基板の中でもＰＥＴ(Ｐｏｌｙｅｔｈｙｌｅｎｅ　ｔｅｒｅｐｈｔｈａｌａｔｅ)フィルムを用いることができれば、コストの面で市場への訴求性が高まると考えられる。しかし、一般にＰＥＴフィルムの耐熱性は、１２０℃程度と言われており、これを超えない温度での熱処理によって十分な導電性、基材との密着性が得られる導電性ペースト、導電性インクの開発が求められている。上記要求を満たすべく種々の提案がなされているが、中でもナノサイズの金属ナノ微粒子が、低温焼結性及び導電性に優れているために、有望視されている。 Although both glass substrates and polymer films can be used for printed electronics, if a PET (Polyethylene terephthalate) film can be used among the film substrates, it is considered that the appeal to the market will increase in terms of cost. . However, in general, the heat resistance of a PET film is said to be about 120 ° C., and a conductive paste or conductive ink that can provide sufficient conductivity and adhesion to a substrate by heat treatment at a temperature not exceeding this temperature. Development is required. Various proposals have been made to satisfy the above requirements, and among these, nano-sized metal nanoparticles are considered promising because they are excellent in low-temperature sinterability and conductivity.
　一般にナノ微粒子とは平均粒子径１ｎｍから１００ｎｍまでのものを言う。特に貴金属のナノ微粒子においては、その高い電気伝導性に加えて表面エネルギーの増大に起因するナノサイズ効果によって溶融温度がバルク金属よりも顕著に低下することから、回路形成プロセス中の処理温度を低下させるために、より平均粒子径の小さいものが志向されてきた。一方で、平均粒子径の小さなナノ微粒子は表面エネルギーの増加により不安定となり容易に凝集してしまうことから、ナノ微粒子の製造時、及び各種導電性インク又は導電性ペースト等の材料として用いる際に沈殿、固液分離等の問題が生じていた。これを防止するため、各種の保護層でナノ微粒子を被覆する技術について種々の検討がなされ、その結果１０ｎｍ以下の極めて微小な金属ナノ微粒子の製造及び利用が可能となった。 Generally, nano-particles mean those with an average particle diameter of 1 nm to 100 nm. Particularly in the case of noble metal nanoparticles, the melting temperature is significantly lower than that of bulk metal due to the nano-size effect due to the increase in surface energy in addition to its high electrical conductivity, thus lowering the processing temperature during the circuit formation process. In order to achieve this, a material having a smaller average particle diameter has been aimed at. On the other hand, nanoparticles with a small average particle size become unstable and easily aggregate due to an increase in surface energy. Therefore, when used as a material such as various conductive inks or conductive pastes during the production of nanoparticles. Problems such as precipitation and solid-liquid separation occurred. In order to prevent this, various studies have been made on techniques for coating nanoparticles with various protective layers. As a result, it has become possible to produce and use extremely minute metal nanoparticles having a size of 10 nm or less.
　特許文献１には、金属ナノ微粒子の製造方法として、酸化銀を原料とし、液相中における還元反応によって、平均粒子径３ｎｍ～２０ｎｍの金属銀微粒子を調製する方法が記載されている。 Patent Document 1 describes a method of preparing metal nanoparticle having a mean particle diameter of 3 nm to 20 nm by a reduction reaction in a liquid phase using silver oxide as a raw material as a method for producing metal nanoparticle.
　特許文献２には、不飽和結合を持つ分子量２００～４００の１級アミンを含む膜で被覆された、平均粒子径ＤTEM：３～２０ｎｍ又はＸ線結晶粒径ＤX：１～２０ｎｍの銀粒子が有機媒体中に単分散した銀粒子分散液と、ヘキシルアミンとを混合する工程（混合工程）、この混合液を撹拌状態で５～８０℃に保持することにより沈降粒子を生成させる工程（沈降工程）、及び固液分離操作により前記沈降粒子を固形分として回収する工程（固液分離工程）を有する製造法が記載されており、実施例で得た銀粒子のＴＥＭ測定による平均粒子径は３～２０ｎｍの銀粒子である。 In Patent Document 2, silver having an average particle diameter D TEM : 3 to 20 nm or an X-ray crystal particle diameter D X : 1 to 20 nm coated with a film containing an unsaturated bond and a primary amine having a molecular weight of 200 to 400 is disclosed. A step of mixing a silver particle dispersion in which particles are monodispersed in an organic medium and hexylamine (mixing step), and a step of generating precipitated particles by maintaining this mixed solution at 5 to 80 ° C. with stirring ( Settling process), and a production method having a process (solid-liquid separation process) of recovering the precipitated particles as a solid content by solid-liquid separation operation is described, and an average particle diameter by TEM measurement of silver particles obtained in Examples Are silver particles of 3 to 20 nm.
　特許文献３には、炭素数が６以上のアルキルアミンと、炭素数が５以下のアルキルアミンとを含むアミン混合液と、金属原子を含む金属化合物を混合して、当該金属化合物とアミンを含む錯化合物を生成する第１工程と、当該錯化合物を加熱することで分解して金属微粒子を生成する第２工程を含むことを特徴とする被覆金属微粒子の製造方法が記載されており、また、得られる銀微粒子が平均粒子径３０ｎｍ以下であることが開示されている。しかし、実施例で得た被覆金属微粒子の透過型電子顕微鏡（ＴＥＭ）及び動的光散乱式（ＤＬＳ）粒子径測定装置によって測定した平均粒子径はすべて２０ｎｍ以下である。 In Patent Document 3, an amine mixed solution containing an alkylamine having 6 or more carbon atoms and an alkylamine having 5 or less carbon atoms and a metal compound containing a metal atom are mixed to contain the metal compound and the amine. There is described a method for producing coated metal fine particles, comprising a first step of producing a complex compound and a second step of decomposing the complex compound by heating to produce metal fine particles, It is disclosed that the obtained silver fine particles have an average particle diameter of 30 nm or less. However, the average particle diameter of the coated metal fine particles obtained in the examples measured by a transmission electron microscope (TEM) and a dynamic light scattering (DLS) particle diameter measuring apparatus is 20 nm or less.
　上記の製造方法には次の問題が残されている。平均粒子径が２０ｎｍ以下の金属ナノ微粒子を製造し導電性インクに用いる場合、導電性インク中で凝集性の高い金属ナノ微粒子を均一に分散させるためには、金属ナノ微粒子の表面が有機分子等で被覆されていることが必要となる。しかし、金属ナノ微粒子の平均粒子径が小さくなるにつれて金属ナノ微粒子の比表面積が大きくなるため、金属ナノ微粒子表面を被覆する有機分子の量が増加する。そのため、当該金属ナノ微粒子を用いて、回路パターン形成した際に回路中に有機分子が残存し、金属ナノ微粒子の本来の導電性を得ることができない。 The following problems remain in the above manufacturing method. When metal nanoparticles having an average particle size of 20 nm or less are produced and used for conductive ink, the surface of the metal nanoparticles is organic molecules or the like in order to uniformly disperse highly cohesive metal nanoparticles in the conductive ink. It is necessary to be coated with. However, since the specific surface area of the metal nanoparticle increases as the average particle diameter of the metal nanoparticle decreases, the amount of organic molecules covering the surface of the metal nanoparticle increases. Therefore, when a circuit pattern is formed using the metal nanoparticles, organic molecules remain in the circuit, and the original conductivity of the metal nanoparticles cannot be obtained.
　そこで、平均粒子径２０ｎｍ以上の金属ナノ微粒子の製造方法として、特許文献４には、金属ナノ粒子（Ａ）と、分散剤（Ｂ）とを含む金属コロイド粒子であって、前記金属ナノ粒子（Ａ）が、数平均粒子径５０ｎｍ以下であり、かつ粒子径１００～２００ｎｍの金属ナノ粒子を含有する金属コロイド粒子と、分散剤（Ｂ）及び／又はその前駆体の存在下、溶媒中で金属化合物を還元して金属コロイド粒子を生成するとともに、金属コロイド粒子の凝集体を沈殿物として生成させる工程と、この工程で生成した凝集体を分離して回収する工程を含む金属コロイド粒子の製造方法が記載されている。しかし、特許文献４に記載の製造方法は、高分子系の分散剤を用いているため、導電性を得るために３００℃程度での熱処理により高分子系の分散剤を除去することが必要となる。そのため、フィルム基材への使用が制限される。 Therefore, as a method for producing metal nanoparticles having an average particle diameter of 20 nm or more, Patent Document 4 discloses metal colloidal particles containing metal nanoparticles (A) and a dispersant (B), wherein the metal nanoparticles ( A) is a metal in a solvent in the presence of metal colloidal particles containing metal nanoparticles having a number average particle size of 50 nm or less and a particle size of 100 to 200 nm, and a dispersant (B) and / or a precursor thereof. A method for producing metal colloidal particles comprising the steps of reducing a compound to produce metal colloidal particles, producing aggregates of metal colloidal particles as precipitates, and separating and recovering the aggregates produced in this step Is described. However, since the manufacturing method described in Patent Document 4 uses a polymer dispersant, it is necessary to remove the polymer dispersant by heat treatment at about 300 ° C. in order to obtain conductivity. Become. Therefore, the use for a film base material is restricted.
特許第４６０７０６６号公報Japanese Patent No. 4660766 特許第５３７１２４７号公報Japanese Patent No. 5371247 特開２０１２－１６２７６７号公報JP 2012-162767 A 特開２０１０－２２９５４４号公報JP 2010-229544 A
　本発明の目的は、金属ナノ微粒子を用いて形成した回路パターンが高い電気伝導性を有するものとなる、平均粒子径約２０ｎｍ以上２００ｎｍ以下の金属ナノ微粒子を効率的に製造することができる製造方法を提供することを課題とする。 An object of the present invention is to provide a production method capable of efficiently producing metal nanoparticles having an average particle diameter of about 20 nm or more and 200 nm or less, wherein a circuit pattern formed using the metal nanoparticles has high electrical conductivity. It is an issue to provide.
　上記課題を解決するために本発明者は研究を重ね、以下の知見を得た。
(i)　金属化合物（ａ）とアミン化合物（ｂ）を含有し、アミン化合物（ｂ）の含有量が、金属化合物（ａ）に含まれる金属原子の物質量１ｍｏｌに対して、０ｍｏｌを超え１ｍｏｌ以下である組成物を反応させることにより、平均粒子径が約２０～２００ｎｍである金属ナノ微粒子を効率よく製造できる。
(ii)　この金属ナノ微粒子を配合した導電性ペースト又はインクは導電性が良い。
(iii)　この金属ナノ微粒子は平均粒子径が大きいために、導電性ペースト又はインクに配合した場合に、比較的短時間又は比較的低温での熱処理で回路などを形成できる。 In order to solve the above-mentioned problems, the present inventor repeated research and obtained the following knowledge.
(i) It contains a metal compound (a) and an amine compound (b), and the content of the amine compound (b) exceeds 0 mol to 1 mol with respect to 1 mol of the metal atom contained in the metal compound (a). By reacting the following composition, metal nanoparticles having an average particle diameter of about 20 to 200 nm can be efficiently produced.
(ii) The conductive paste or ink containing the metal nanoparticles has good conductivity.
(iii) Since the metal nanoparticle has a large average particle size, a circuit or the like can be formed by heat treatment at a relatively short time or at a relatively low temperature when blended in a conductive paste or ink.
　本発明は、上記知見に基づき完成されたものであり、下記の製造方法を提供する。
項１．　金属化合物（ａ）とアミン化合物（ｂ）を含有する組成物を反応させる金属ナノ微粒子の製造方法であって、組成物中のアミン化合物（ｂ）の含有量が、金属化合物（ａ）に含まれる金属原子の物質量１ｍｏｌに対して、０ｍｏｌを超え１ｍｏｌ以下の範囲であることを特徴とする方法。
項２．　組成物が、さらに、２０℃の水に対して１ｇ／Ｌ以上溶解する有機溶媒（ｃ）を含有する項１に記載の製造方法。
項３．　有機溶媒（ｃ）が、エーテル結合とヒドロキシル基を有する溶媒を含む項２に記載の製造方法。
項４．　有機溶媒（ｃ）が、グリコールエーテル類、及びアルコキシ基を有するアルコール類からなる群より選ばれる少なくとも１種の溶媒を含む項２又は３に記載の製造方法。
項５．　金属化合物（ａ）が、蓚酸金属塩である項１～４のいずれかに記載の製造方法。
項６．　アミン化合物（ｂ）が、第１級アミン、及び第１級アミンと第３級アミンを有するジアミン化合物からなる群より選ばれる少なくとも１種である項１～５のいずれかに記載の製造方法。
項７．　組成物が、さらに、脂肪酸（ｄ）を含有する項１～６のいずれかに記載の製造方法。
項８．　組成物中の脂肪酸の含有量が、金属化合物（ａ）１重量部に対して、０．１重量部以上１５重量部以下である項７に記載の製造方法。
項９．　反応が、５０℃以上２５０℃以下の温度での熱分解反応である項１～８のいずれかに記載の製造方法。
項１０．　項１～９のいずれかに記載の製造方法により得られた平均粒子径が２０ｎｍ以上２００ｎｍ以下の金属ナノ微粒子。
項１１．　項１～９のいずれかに記載の製造方法により得られた金属ナノ微粒子を含有する導電性インク組成物、又は導電性ペースト。
項１２．　項１１に記載の導電性インク組成物、又は導電性ペーストを用いて形成された回路配線又は電極。 The present invention has been completed based on the above findings and provides the following production method.
Item 1. It is a manufacturing method of the metal nanoparticle which makes the composition containing a metal compound (a) and an amine compound (b) react, Comprising: Content of the amine compound (b) in a composition is contained in a metal compound (a) The method is characterized by being in the range of more than 0 mol and not more than 1 mol with respect to 1 mol of the metal atom.
Item 2. Item 2. The method according to Item 1, wherein the composition further comprises an organic solvent (c) that dissolves 1 g / L or more in water at 20 ° C.
Item 3. Item 3. The production method according to Item 2, wherein the organic solvent (c) comprises a solvent having an ether bond and a hydroxyl group.
Item 4. Item 4. The method according to Item 2 or 3, wherein the organic solvent (c) contains at least one solvent selected from the group consisting of glycol ethers and alcohols having an alkoxy group.
Item 5. Item 5. The production method according to any one of Items 1 to 4, wherein the metal compound (a) is a metal oxalate salt.
Item 6. Item 6. The production method according to any one of Items 1 to 5, wherein the amine compound (b) is at least one selected from the group consisting of a primary amine and a diamine compound having a primary amine and a tertiary amine.
Item 7. Item 7. The production method according to any one of Items 1 to 6, wherein the composition further contains a fatty acid (d).
Item 8. Item 8. The method according to Item 7, wherein the content of the fatty acid in the composition is from 0.1 parts by weight to 15 parts by weight with respect to 1 part by weight of the metal compound (a).
Item 9. Item 9. The production method according to any one of Items 1 to 8, wherein the reaction is a thermal decomposition reaction at a temperature of 50 ° C. or higher and 250 ° C. or lower.
Item 10. Item 10. A metal nanoparticle having an average particle size of 20 nm to 200 nm obtained by the production method according to any one of Items 1 to 9.
Item 11. Item 10. A conductive ink composition or a conductive paste containing metal nanoparticles obtained by the production method according to any one of Items 1 to 9.
Item 12. Item 12. A circuit wiring or electrode formed using the conductive ink composition according to Item 11, or a conductive paste.
　本発明によれば、金属化合物（ａ）とアミン化合物（ｂ）を含有し、アミン化合物（ｂ）を金属化合物（ａ）に含まれる金属原子の物質量１ｍｏｌに対して、約０ｍｏｌを超え１ｍｏｌ以下の範囲で含む組成物を反応させることにより、従来よりも平均粒子径の大きな金属ナノ微粒子を効率よく製造することが可能となる。さらに、本発明によって製造された金属ナノ微粒子を用いて導電性インク、又は導電性ペーストを製造した際に、導電性ペースト中で金属ナノ微粒子の分散安定性が良好である。また、本発明方法により得られる金属ナノ微粒子は表面を被覆する有機分子の残存量が少ないため、この金属ナノ微粒子を含む導電性インク又はペーストを用いることにより、短時間又は比較的低温での熱処理のみで高い電気伝導性を示す回路パターンや電極が得られる。従って、本発明は、極めて優れたプリンテッドエレクトロニクス用材料を提供できる。 According to the present invention, the metal compound (a) and the amine compound (b) are contained, and the amine compound (b) exceeds about 0 mol and 1 mol with respect to 1 mol of the metal atom contained in the metal compound (a). By reacting the composition contained in the following range, it is possible to efficiently produce metal nanoparticles having a larger average particle diameter than before. Furthermore, when the conductive ink or conductive paste is manufactured using the metal nanoparticle manufactured according to the present invention, the dispersion stability of the metal nanoparticle in the conductive paste is good. In addition, since the metal nanoparticles obtained by the method of the present invention have a small amount of remaining organic molecules covering the surface, heat treatment can be performed in a short time or at a relatively low temperature by using a conductive ink or paste containing the metal nanoparticles. A circuit pattern or an electrode exhibiting high electrical conductivity can be obtained only by the above. Therefore, the present invention can provide an extremely excellent printed electronics material.
実施例４で得られた銀ナノ微粒子のＳＥＭ（走査型電子顕微鏡）写真である。4 is a SEM (scanning electron microscope) photograph of silver nanoparticles obtained in Example 4. 実施例５で得られた銀ナノ微粒子のＳＥＭ（走査型電子顕微鏡）写真である。4 is a SEM (scanning electron microscope) photograph of silver nanoparticles obtained in Example 5. 比較例１で得られた銀ナノ微粒子のＳＥＭ（走査型電子顕微鏡）写真である。2 is a SEM (scanning electron microscope) photograph of silver nanoparticles obtained in Comparative Example 1. 比較例２で得られた銀ナノ微粒子のＳＥＭ（走査型電子顕微鏡）写真である。4 is a SEM (scanning electron microscope) photograph of silver nanoparticles obtained in Comparative Example 2.
　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
金属ナノ微粒子の製造方法に用いる組成物
　本発明の製造方法に用いる組成物は、金属化合物（ａ）とアミン化合物（ｂ）を含有し、組成物中のアミン化合物（ｂ）の含有量が、金属化合物（ａ）に含まれる金属原子の物質量１ｍｏｌに対して、約０ｍｏｌを超え１ｍｏｌ以下の範囲であることを特徴とする。上記組成物を本発明の製造方法に用いることにより、平均粒子径が約２０ｎｍ以上２００ｎｍ以下（例えば、約２０ｎｍ以上１５０ｎｍ以下であり、特に、約２０ｎｍ以上１００ｎｍ以下）の範囲である金属ナノ微粒子を製造することができる。 Composition used in the method for producing metal nanoparticles The composition used in the production method of the present invention contains a metal compound (a) and an amine compound (b), and the content of the amine compound (b) in the composition is: It is characterized by being in the range of more than about 0 mol and 1 mol or less with respect to 1 mol of the metal atom contained in the metal compound (a). By using the above composition in the production method of the present invention, metal nanoparticles having an average particle size of about 20 nm to 200 nm (for example, about 20 nm to 150 nm, particularly about 20 nm to 100 nm) are obtained. Can be manufactured.
　なお、本発明における金属ナノ微粒子の平均粒子径は、走査型電子顕微鏡（ＳＥＭ）の画像から測定される２０個の微粒子の長辺の平均値（ＤＳＥＭ）である。本発明では、ＤＳＥＭが約２０ｎｍ以上２００ｎｍ以下（例えば、約２０ｎｍ以上１５０ｎｍ以下であり、特に、約２０ｎｍ以上１００ｎｍ以下）である金属ナノ微粒子が好ましい。上記平均粒子径範囲の金属ナノ微粒子は、良好な導電性を有する導電性インク、又は導電性ペーストを作製する上で有利である。 In addition, the average particle diameter of the metal nanoparticle in the present invention is an average value (D SEM ) of long sides of 20 particles measured from an image of a scanning electron microscope (SEM). In the present invention, metal nanoparticles having a DSEM of about 20 nm to 200 nm (for example, about 20 nm to 150 nm, particularly about 20 nm to 100 nm) are preferable. The metal nanoparticles in the above average particle diameter range are advantageous for producing a conductive ink or a conductive paste having good conductivity.
　本発明の製造方法に用いる組成物は、さらに有機溶媒（ｃ）を含有してもよい。組成物が有機溶媒（ｃ）を含有することにより、金属化合物（ａ）とアミン化合物（ｂ）を組成物中で均一に混合させ易くなり、熱分解反応が効率的に進行し、効率的に金属ナノ微粒子が生成する。 The composition used in the production method of the present invention may further contain an organic solvent (c). When the composition contains the organic solvent (c), it becomes easy to uniformly mix the metal compound (a) and the amine compound (b) in the composition, the thermal decomposition reaction proceeds efficiently, and efficiently. Metal nanoparticles are generated.
　本発明で得られる金属ナノ微粒子は、導電性インク、又は導電性ペースト中で凝集を防止し、所望の溶媒中で良好に分散させるために、金属ナノ微粒子の表面が保護層で被覆されていることが必要である。そのために、本発明の製造方法に用いる組成物は、金属化合物（ａ）と共に、保護層となり得るアミン化合物（ｂ）を含有している。 The metal nanoparticles obtained in the present invention are coated with a protective layer on the surface of the metal nanoparticles in order to prevent aggregation in the conductive ink or conductive paste and to disperse them well in a desired solvent. It is necessary. Therefore, the composition used for the production method of the present invention contains an amine compound (b) that can be a protective layer together with the metal compound (a).
　本発明の製造方法に用いる組成物は、必要に応じて、本発明の効果に影響を与えない範囲で、プリンテッドエレクトロニクスに適用される金属微粒子用の添加剤を含有させることが可能である。具体的な添加剤としては、脂肪酸（ｄ）、粘度調製剤、導電助剤、チョーキング防止剤、酸化防止剤、ｐＨ調製剤、乾燥防止剤、密着付与剤、防腐剤、消泡剤、レベリング剤、界面活性剤等を例示することができる。 The composition used in the production method of the present invention can contain an additive for fine metal particles applied to printed electronics as required, as long as the effect of the present invention is not affected. Specific additives include fatty acid (d), viscosity adjusting agent, conductive additive, anti-choking agent, antioxidant, pH adjusting agent, anti-drying agent, adhesion promoter, antiseptic, antifoaming agent, leveling agent. And surfactants.
金属化合物（ａ）
　本発明の製造方法に用いる金属化合物（ａ）として、金属のカルボン酸塩のような有機金属塩；金属のスルホン酸塩、チオール塩、塩化物、硝酸塩、又は炭酸塩のような無機金属塩等を例示することができる。中でも、金属ナノ微粒子が生成した後、対イオン由来の物質の除去が容易である点で、有機金属塩及び炭酸塩が好ましく、有機金属塩がより好ましく、中でも、蟻酸、酢酸、蓚酸、マロン酸、安息香酸、フタル酸等のカルボン酸塩がより好ましく、熱分解の容易さの点から、蓚酸塩がさらにより好ましい。
　金属化合物は、単独で、または２種以上を組み合わせて用いることができる。金属化合物（ａ）は、市販品を購入して用いることができる。 Metal compound (a)
As the metal compound (a) used in the production method of the present invention, an organic metal salt such as a metal carboxylate; an inorganic metal salt such as a metal sulfonate, thiol salt, chloride, nitrate, or carbonate Can be illustrated. Among them, organic metal salts and carbonates are preferable, and organic metal salts are more preferable in that it is easy to remove counterion-derived substances after the formation of metal nanoparticles, and formic acid, acetic acid, oxalic acid, malonic acid are particularly preferable. Carboxylic acid salts such as benzoic acid and phthalic acid are more preferred, and oxalates are even more preferred from the viewpoint of easiness of thermal decomposition.
A metal compound can be used individually or in combination of 2 or more types. A commercial item can be purchased and used for a metal compound (a).
　金属化合物（ａ）の金属種としては、金、銀、銅、白金、パラジウム、ニッケル、アルミニウム等を例示することができる。中でも、導電性、及び耐酸化性の点で、金、銀、白金が好ましく、コスト及び低温焼結性の点で、銀がより好ましい。また、銅、ニッケル、アルミニウムも好ましい。 Examples of the metal species of the metal compound (a) include gold, silver, copper, platinum, palladium, nickel, and aluminum. Of these, gold, silver, and platinum are preferable in terms of conductivity and oxidation resistance, and silver is more preferable in terms of cost and low-temperature sinterability. Copper, nickel, and aluminum are also preferable.
　本発明の金属化合物（ａ）として、蟻酸金、蟻酸銀、蟻酸銅、蟻酸白金、蟻酸パラジウム、蟻酸ニッケル、蟻酸アルミニウム、酢酸金、酢酸銀、酢酸銅、酢酸白金、酢酸パラジウム、酢酸ニッケル、酢酸アルミニウム、蓚酸金、蓚酸銀、蓚酸銅、蓚酸白金、蓚酸パラジウム、蓚酸ニッケル、蓚酸アルミニウム、マロン酸金、マロン酸銀、マロン酸銅、マロン酸白金、マロン酸パラジウム、マロン酸ニッケル、マロン酸アルミニウム、フタル酸金、フタル酸銀、フタル酸銅、フタル酸白金、フタル酸パラジウム、フタル酸ニッケル、フタル酸アルミニウム等を例示できる。中でも、蓚酸銀、蓚酸銅、蓚酸ニッケル、蓚酸アルミニウム等が好ましい。
　組成物中の金属化合物（ａ）の含有量は、組成物の全体に対して、１重量％以上が好ましく、１０重量％以上がより好ましく、２０重量％以上がさらにより好ましい。また、９５重量％以下が好ましく、８０重量％以下がより好ましく、７０重量％以下がさらにより好ましい。
　組成物中の金属化合物（ａ）の含有量としては、約１～９５重量％、約１～８０重量％、約１～７０重量％、約１０～９５重量％、約１０～８０重量％、約１０～７０重量％、約２０～９５重量％、約２０～８０重量％、約２０～７０重量％が挙げられる。上記範囲内であれば、本発明の効果を十分に得ることができる。 As the metal compound (a) of the present invention, gold formate, silver formate, copper formate, platinum formate, palladium formate, nickel formate, aluminum formate, gold acetate, silver acetate, copper acetate, platinum acetate, palladium acetate, nickel acetate, acetic acid Aluminum, gold oxalate, silver oxalate, copper oxalate, platinum oxalate, palladium oxalate, nickel oxalate, aluminum oxalate, gold malonate, silver malonate, copper malonate, platinum malonate, palladium malonate, nickel malonate, aluminum malonate Examples thereof include gold phthalate, silver phthalate, copper phthalate, platinum phthalate, palladium phthalate, nickel phthalate, and aluminum phthalate. Of these, silver oxalate, copper oxalate, nickel oxalate, aluminum oxalate and the like are preferable.
The content of the metal compound (a) in the composition is preferably 1% by weight or more, more preferably 10% by weight or more, and still more preferably 20% by weight or more based on the entire composition. Moreover, 95 weight% or less is preferable, 80 weight% or less is more preferable, and 70 weight% or less is still more preferable.
The content of the metal compound (a) in the composition is about 1 to 95% by weight, about 1 to 80% by weight, about 1 to 70% by weight, about 10 to 95% by weight, about 10 to 80% by weight, Examples include about 10 to 70% by weight, about 20 to 95% by weight, about 20 to 80% by weight, and about 20 to 70% by weight. If it is in the said range, the effect of this invention can fully be acquired.
アミン化合物（ｂ）
　本発明の製造方法に用いるアミン化合物（ｂ）は、金属化合物（ａ）と結合する能力を有し、かつ金属ナノ微粒子が生成した際に、金属ナノ微粒子の表面上で保護層を形成し得るものであれば、制限なく用いることができる。
　例えば、アンモニアの３個の水素原子のうち、１個を直鎖、分岐、または環状の炭化水素基で置換した化合物である第１級アミン化合物（ｂ－１）、２個を同様に置換した第２級アミン化合物（ｂ－２）、及び３個を同様に置換した第３級アミン化合物（ｂ－３）を例示することができる。中でも、金属化合物（ａ）と結合する能力が高く、また得られた金属ナノ微粒子を用いた導電性インク、又は導電性ペーストを基板上に塗布した際、比較的低温（例えば、１２０℃以下）の熱処理によって金属ナノ微粒子表面から容易に脱離する点で、第１級アミン化合物（ｂ－１）が好ましい。 Amine compound (b)
The amine compound (b) used in the production method of the present invention has an ability to bind to the metal compound (a), and can form a protective layer on the surface of the metal nanoparticle when the metal nanoparticle is generated. Anything can be used without limitation.
For example, among the three hydrogen atoms of ammonia, two primary amine compounds (b-1), which are compounds in which one is substituted with a linear, branched, or cyclic hydrocarbon group, are similarly substituted. Examples include the secondary amine compound (b-2) and the tertiary amine compound (b-3) in which three are similarly substituted. Among them, the ability to bind to the metal compound (a) is high, and when a conductive ink or conductive paste using the obtained metal nanoparticles is applied on a substrate, the temperature is relatively low (for example, 120 ° C. or lower). The primary amine compound (b-1) is preferable in that it is easily detached from the surface of the metal nanoparticle by the heat treatment.
　第１級アミン化合物（ｂ－１）としては、エチルアミン、ｎ-プロピルアミン、イソプロピルアミン、１,２-ジメチルプロピルアミン、ｎ-ブチルアミン、イソブチルアミン、ｓｅｃ-ブチルアミン、ｔｅｒｔ-ブチルアミン、イソアミルアミン、ｔｅｒｔ-アミルアミン、３-ペンチルアミン、ｎ-アミルアミン、ｎ-ヘキシルアミン、ｎ-ヘプチルアミン、ｎ-オクチルアミン、２-オクチルアミン、ｔｅｒｔ-オクチルアミン、２-エチルヘキシルアミン、ｎ-ノニルアミン、ｎ-アミノデカン、ｎ-アミノウンデカン、ｎ-ドデシルアミン、ｎ-トリデシルアミン、２-トリデシルアミン、ｎ-テトラデシルアミン、ｎ-ペンタデシルアミン、ｎ-ヘキサデシルアミン、ｎ-ヘプタデシルアミン、ｎ-オクタデシルアミン、ｎ-オレイルアミン等の直鎖又は分岐炭化水素基を有するアルキルアミン等を例示することができる。また、脂環式アミンであるシクロプロピルアミン、シクロブチルアミン、シクロプロピルアミン、シクロヘキシルアミン、シクロヘプチルアミン、シクロオクチルアミンや、芳香族アミンであるアニリン等も例示することができる。さらに、３-イソプロポキシプロピルアミン、イソブトキシプロピルアミン等のエーテルアミンも例示することができる。 Examples of the primary amine compound (b-1) include ethylamine, n-propylamine, isopropylamine, 1,2-dimethylpropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, isoamylamine, tert -Amylamine, 3-pentylamine, n-amylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-octylamine, tert-octylamine, 2-ethylhexylamine, n-nonylamine, n-aminodecane, n-aminoundecane, n-dodecylamine, n-tridecylamine, 2-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine Linear or branched hydrocarbons such as n-oleylamine It can be exemplified an alkyl amine having a group. Moreover, cyclopropylamine, cyclobutylamine, cyclopropylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine that are alicyclic amines, aniline that is an aromatic amine, and the like can also be exemplified. Further, ether amines such as 3-isopropoxypropylamine and isobutoxypropylamine can also be exemplified.
　第２級アミン化合物（ｂ－２）としては、Ｎ，Ｎ-ジプロピルアミン、Ｎ，Ｎ-ジブチルアミン、Ｎ，Ｎ-ジペンチルアミン、Ｎ，Ｎ-ジヘキシルアミン、Ｎ，Ｎ-ジペプチルアミン、Ｎ，Ｎ-ジオクチルアミン、Ｎ，Ｎ-ジノニルアミン、Ｎ，Ｎ-ジデシルアミン、Ｎ，Ｎ-ジウンデシルアミン、Ｎ，Ｎ-ジドデシルアミン、Ｎ，Ｎ-ジステアリルアミン、Ｎ-メチル-Ｎ-プロピルアミン、Ｎ-エチル-Ｎ-プロピルアミン、Ｎ-プロピル-Ｎ-ブチルアミン等のジアルキルモノアミン、およびピペリジン等の環状アミンを例示することができる。 As the secondary amine compound (b-2), N, N-dipropylamine, N, N-dibutylamine, N, N-dipentylamine, N, N-dihexylamine, N, N-dipeptylamine, N, N-dioctylamine, N, N-dinonylamine, N, N-didecylamine, N, N-diundecylamine, N, N-didodecylamine, N, N-distearylamine, N-methyl-N-propylamine, Examples thereof include dialkyl monoamines such as N-ethyl-N-propylamine and N-propyl-N-butylamine, and cyclic amines such as piperidine.
　第３級アミン化合物（ｂ－３）としては、トリエチルアミン、トリブチルアミン、トリヘキシルアミン、ジメチルオクチルアミン、ジメチルデシルアミン、ジメチルラウリルアミン、ジメチルミリスチルアミン、ジメチルパルミチルアミン、ジメチルステアリルアミン、ジラウリルモノメチルアミン等を例示することができる。 As the tertiary amine compound (b-3), triethylamine, tributylamine, trihexylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dilaurylmonomethyl An amine etc. can be illustrated.
　さらに、本発明では、ひとつの化合物中に２つのアミノ基を有するジアミン化合物（ｂ－４）も用いることができる。ジアミン化合物（ｂ－４）としては、エチレンジアミン、Ｎ，Ｎ-ジメチルエチレンジアミン、Ｎ，Ｎ’-ジメチルエチレンジアミン、Ｎ，Ｎ-ジエチルエチレンジアミン、Ｎ，Ｎ’-ジエチルエチレンジアミン、１，３-プロパンジアミン、２，２-ジメチル-１，３-プロパンジアミン、Ｎ，Ｎ-ジメチル‐１，３‐プロパンジアミン、Ｎ，Ｎ’‐ジメチル-１，３-プロパンジアミン、Ｎ，Ｎ-ジエチル-１，３-プロパンジアミン、Ｎ，Ｎ’-ジエチル-１，３-プロパンジアミン、１，４-ブタンジアミン、Ｎ，Ｎ-ジメチル-１，４-ブタンジアミン、Ｎ，Ｎ’-ジメチル-１，４-ブタンジアミン、Ｎ，Ｎ-ジエチル-１，４-ブタンジアミン、Ｎ，Ｎ’-ジエチル-１，４-ブタンジアミン、１，５-ペンタンジアミン、１，５-ジアミノ-２-メチルペンタン、１，６-ヘキサンジアミン、Ｎ，Ｎ-ジメチル-１，６-ヘキサンジアミン、Ｎ，Ｎ’-ジメチル-１，６-ヘキサンジアミン、１，７-ヘプタンジアミン、１，８-オクタンジアミン等を例示することができる。 Furthermore, in the present invention, a diamine compound (b-4) having two amino groups in one compound can also be used. Examples of the diamine compound (b-4) include ethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, 1,3-propanediamine, , 2-Dimethyl-1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N'-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propane Diamine, N, N′-diethyl-1,3-propanediamine, 1,4-butanediamine, N, N-dimethyl-1,4-butanediamine, N, N′-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N′-diethyl-1,4-butanediamine, 1,5-pentanediamine, 1,5-diamino-2-methylpentane, 1,6-he Examples include sundiamine, N, N-dimethyl-1,6-hexanediamine, N, N′-dimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, and the like. .
　ジアミン化合物（ｂ－４）の中でも、アミンの一方が第１級アミン、他方が第３級アミンであるジアミン化合物は、金属化合物（ａ）との結合能に優れ、金属ナノ微粒子が生成した際に、金属ナノ微粒子の表面上で保護層を形成し易い点で好ましい。一方が第１級アミン、他方が第３級アミンであるジアミン化合物としては、Ｎ，Ｎ-ジメチルエチレンジアミン、Ｎ，Ｎ-ジエチルエチレンジアミン、Ｎ，Ｎ-ジメチル-１，３-プロパンジアミン、Ｎ，Ｎ-ジエチル-１，３-プロパンジアミン、Ｎ，Ｎ-ジメチル-１，４-ブタンジアミン、Ｎ，Ｎ-ジエチル-１，４-ブタンジアミン、Ｎ，Ｎ-ジメチル-１，６-ヘキサンジアミン等を例示することができる。 Among the diamine compounds (b-4), a diamine compound in which one of the amines is a primary amine and the other is a tertiary amine is excellent in binding ability with the metal compound (a), and metal nanoparticles are formed. Moreover, it is preferable in that a protective layer can be easily formed on the surface of the metal nanoparticle. Examples of diamine compounds in which one is a primary amine and the other is a tertiary amine include N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-propanediamine, and N, N. -Diethyl-1,3-propanediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dimethyl-1,6-hexanediamine, etc. It can be illustrated.
　上述したアミン化合物（ｂ）の中でも、金属ナノ微粒子を導電性インク、又は導電性ペーストとして用いた際の溶媒中での分散安定性、及び回路形成時に、低温の熱処理で容易に脱離可能な点で、ｎ-プロピルアミン、イソプロピルアミン、シクロプロピルアミン、ｎ-ブチルアミン、イソブチルアミン、ｓｅｃ-ブチルアミン、ｔｅｒｔ-ブチルアミン、シクロブチルアミン、ｎ-アミルアミン、ｎ-ヘキシルアミン、シクロヘキシルアミン、ｎ-オクチルアミン、２-エチルヘキシルアミン、ｎ-ドデシルアミン、ｎ-オレイルアミン、Ｎ,Ｎ-ジメチル-１，３-プロパンジアミンが好ましく、ｎ-ブチルアミン、ｎ-ヘキシルアミン、シクロヘキシルアミン、ｎ-オクチルアミン、ｎ-ドデシルアミン、Ｎ,Ｎ-ジメチル-１，３-プロパンジアミンがより好ましい。
　アミン化合物（ｂ）は、１種を単独で、又は２種以上を組み合わせて用いることができる。具体的には、（ｂ-１）、（ｂ-２）、（ｂ-３）、（ｂ-４）の中の１つ以上を使用することができ、特に、（ｂ-１）のみ、（ｂ-４）のみ、及び（ｂ-１）と（ｂ-４）との組み合わせが好ましい。さらに、（ｂ-１）、（ｂ-２）、（ｂ-３）、（ｂ-４）の各群の中でも１種以上を使用することができる。 Among the amine compounds (b) described above, dispersion stability in a solvent when metal nanoparticles are used as a conductive ink or conductive paste, and can be easily detached by low-temperature heat treatment during circuit formation. N-propylamine, isopropylamine, cyclopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, cyclobutylamine, n-amylamine, n-hexylamine, cyclohexylamine, n-octylamine, 2-ethylhexylamine, n-dodecylamine, n-oleylamine, N, N-dimethyl-1,3-propanediamine are preferred, n-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, n-dodecylamine N, N-dimethyl-1,3-propanediamine is more preferable. .
An amine compound (b) can be used individually by 1 type or in combination of 2 or more types. Specifically, one or more of (b-1), (b-2), (b-3), and (b-4) can be used, in particular, only (b-1), Only (b-4) and a combination of (b-1) and (b-4) are preferred. Furthermore, 1 or more types can be used among each group of (b-1), (b-2), (b-3), (b-4).
　組成物中のアミン化合物（ｂ）の含有量は、金属化合物（ａ）に含まれる金属原子の物質量１ｍｏｌに対して、約０ｍｏｌを超えて１ｍｏｌ以下の範囲であればよい。アミン化合物（ｂ）の含有量は、金属化合物（ａ）に含まれる金属原子の物質量１ｍｏｌに対して、０．１ｍｏｌ以上が好ましく、０．２ｍｏｌ以上がより好ましく、０．３ｍｏｌ以上がさらにより好ましく、０．４ｍｏｌ以上がさらにより好ましい。また、アミン化合物（ｂ）の含有量は、金属化合物（ａ）に含まれる金属原子の物質量１ｍｏｌに対して、０．９ｍｏｌ以下が好ましく、０．８ｍｏｌ以下がより好ましい。上記範囲内であれば、本発明の効果を十分に得ることができる。
　組成物中の、金属化合物（ａ）に含まれる金属原子の物質量１ｍｏｌに対するアミン化合物（ｂ）の含有量としては、約０ｍｏｌを超え１ｍｏｌ以下、約０．１ｍｏｌ以上１ｍｏｌ以下、約０．２ｍｏｌ以上１ｍｏｌ以下、約０．３ｍｏｌ以上１ｍｏｌ以下、約０．４ｍｏｌ以上１ｍｏｌ以下、約０．１ｍｏｌ以上０．９ｍｏｌ以下、約０．２ｍｏｌ以上０．９ｍｏｌ以下、約０．３ｍｏｌ以上０．９ｍｏｌ以下、約０．４ｍｏｌ以上０．９ｍｏｌ以下、約０．１ｍｏｌ以上０．８ｍｏｌ以下、約０．２ｍｏｌ以上０．８ｍｏｌ以下、約０．３ｍｏｌ以上０．８ｍｏｌ以下、約０．４ｍｏｌ以上０．８ｍｏｌ以下が挙げられる。
　なお、製造に用いる組成物中に含まれるアミン化合物（ｂ）は、得られた金属ナノ微粒子を配合した導電性インク、又は導電性ペーストを熱処理に付して回路パターン（導電膜）を形成する際の熱処理によって、アミン化合物（ｂ）のほとんどが金属ナノ微粒子の表面から脱離するため、組成物中にアミン化合物（ｂ）を多量に添加しても回路パターンを形成した際の塗膜の導電性にほとんど影響を与えない。 The content of the amine compound (b) in the composition may be in the range of more than about 0 mol and 1 mol or less with respect to 1 mol of the metal atom contained in the metal compound (a). The content of the amine compound (b) is preferably 0.1 mol or more, more preferably 0.2 mol or more, even more preferably 0.3 mol or more, with respect to 1 mol of the metal atom contained in the metal compound (a). Preferably, 0.4 mol or more is even more preferable. Moreover, 0.9 mol or less is preferable with respect to 1 mol of substance amounts of the metal atom contained in a metal compound (a), and, as for content of an amine compound (b), 0.8 mol or less is more preferable. If it is in the said range, the effect of this invention can fully be acquired.
In the composition, the content of the amine compound (b) with respect to 1 mol of the metal atom contained in the metal compound (a) is more than about 0 mol and 1 mol or less, about 0.1 mol or more and 1 mol or less, about 0.2 mol. 1 mol or less, about 0.3 mol to 1 mol, about 0.4 mol to 1 mol, about 0.1 mol to 0.9 mol, about 0.2 mol to 0.9 mol, about 0.3 mol to 0.9 mol, About 0.4 mol to 0.9 mol, about 0.1 mol to 0.8 mol, about 0.2 mol to 0.8 mol, about 0.3 mol to 0.8 mol, about 0.4 mol to 0.8 mol Can be mentioned.
The amine compound (b) contained in the composition used for production forms a circuit pattern (conductive film) by subjecting the conductive ink or conductive paste containing the obtained metal nanoparticles to heat treatment. Since most of the amine compound (b) is desorbed from the surface of the metal nanoparticle by the heat treatment, the coating film when the circuit pattern is formed even if a large amount of the amine compound (b) is added to the composition. Almost no influence on conductivity.
　本発明におけるアミン化合物（ｂ）の物質量（ｍｏｌ）は、アンモニアの３個の水素原子のうち１個、２個、又は３個を炭化水素基で置換した第１級アミン化合物（ｂ－１）、第２級アミン化合物（ｂ－２）、又は第３級アミン化合物（ｂ－３）では、金属化合物（ａ）に配位する部位である第１級アミン、第２級アミン、又は第３級アミンの数を基準として算出する。即ち、分子のモル数を物質量（ｍｏｌ）とする。 The substance amount (mol) of the amine compound (b) in the present invention is the primary amine compound (b-1) in which one, two, or three of the three hydrogen atoms of ammonia are substituted with a hydrocarbon group. ), Secondary amine compound (b-2), or tertiary amine compound (b-3), the primary amine, secondary amine, or secondary site that is coordinated to the metal compound (a) Calculation is based on the number of tertiary amines. That is, the number of moles of molecules is defined as a substance amount (mol).
　また、アミン化合物（ｂ）の物質量（ｍｏｌ）は、第１級アミン及び／又は第２級アミンを有するジアミン化合物（ｂ－４）では、第１級アミン及び第２級アミンの数を基準とする。即ち、第１級アミン若しくは第２級アミンを２個、又は第１級アミンと第２級アミンをそれぞれ１個ずつ有するジアミン化合物の物質量（ｍｏｌ）は、分子のモル数の２倍となる。
　また、アミン化合物（ｂ）の物質量（ｍｏｌ）は、一方が第１級アミン若しくは第２級アミン、他方が第３級アミンであるジアミン化合物では、第１級アミン又は第２級アミンの数を基準として算出する。即ち、分子のモル数が物質量（ｍｏｌ）となる。これは、第３級アミンは立体障害が大きく金属化合物（ａ）との配位が困難であるため、金属化合物（ａ）との配位が容易である第１級アミン又は第２級アミンの数を基準とするのが適切だからである。 The amount (mol) of the amine compound (b) is based on the number of primary amines and secondary amines in the diamine compound (b-4) having primary amines and / or secondary amines. And That is, the substance amount (mol) of a diamine compound having two primary amines or two secondary amines, or one primary amine and one secondary amine, is twice the number of moles of the molecule. .
The amount (mol) of the amine compound (b) is the number of primary amines or secondary amines in the case of a diamine compound in which one is a primary amine or secondary amine and the other is a tertiary amine. Is calculated based on That is, the number of moles of molecules is the amount of substance (mol). This is because the tertiary amine has a large steric hindrance and is difficult to coordinate with the metal compound (a), so that the primary amine or the secondary amine can be easily coordinated with the metal compound (a). This is because it is appropriate to use numbers as the basis.
有機溶媒（ｃ）
　有機溶媒（ｃ）は、それには限定されないが、２０℃の水に対して約１ｇ／Ｌ以上溶解するものが好ましく、約１０ｇ／Ｌ以上溶解するものがより好ましい。１つの化合物（有機溶媒）の中にエーテル結合とヒドロキシル基の両方の官能基を有する有機溶媒を好適に使用できる。この有機化合物は、エーテル結合以外の結合、及びヒドロキシル基以外の官能基を有していても良い。 Organic solvent (c)
The organic solvent (c) is not limited thereto, but preferably dissolves in an amount of about 1 g / L or more in water at 20 ° C., more preferably dissolves in an amount of about 10 g / L or more. An organic solvent having both an ether bond and a hydroxyl group in one compound (organic solvent) can be preferably used. This organic compound may have a bond other than an ether bond and a functional group other than a hydroxyl group.
　有機溶媒（ｃ）としては、ベンゼン、ベンゾニトリル等の芳香族化合物、アセトン、アセチルアセトン、メチルエチルケトン等のケトン類、酢酸エチル、酢酸ブチル、酪酸エチル、蟻酸エチル等の脂肪酸エステル類、ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、１，４-ジオキサン等のエーテル類、ジクロロメタン、クロロホルム、ジクロロエタン等のハロゲン化炭化水素類、１，２-プロパンジオール、１，２-ブタンジオール、１，３-ブタンジオール、１，４-ブタンジオール、２，３-ブタンジオール、１，２-ヘキサンジオール、１，６-ヘキサンジオール、１，２-ペンタンジオール、１，５-ペンタンジオール、２-メチル-２，４-ペンタンジオール、３-メチル-１，５-ペンタンジオール等のジオール類、炭素数１～７の直鎖又は分岐アルキルを有するアルコール、シクロヘキサノール、３-メトキシ-３-メチル-１-ブタノール、３-メトキシ-１-ブタノール等のアルコール類、ポリエチレングリコール、トリエチレングリコールモノメチルエーテル、テトラエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、３-メトキシブチルアセテート、エチレングリコールモノブチルエーテル、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノプロピルエーテル、トリプロピレングリコールモノブチルエーテル等のグリコールもしくはグリコールエーテル類、メチル-ｎ-アミルケトン、メチルエチルケトンオキシム、トリアセチン、γ-ブチロラクトン、２-ピロリドン、Ｎ-メチルピロリドン、アセトニトリル、Ｎ，Ｎ-ジメチルホルムアミド、Ｎ-(２-アミノエチル)ピペラジン、ジメチルスルホキシド、及びテルピネオール等のテルペン類などを例示することができる。
　有機溶媒（ｃ）は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。有機溶媒（ｃ）を用いて組成物の粘度を適宜調整することが可能である。 Examples of the organic solvent (c) include aromatic compounds such as benzene and benzonitrile, ketones such as acetone, acetylacetone, and methyl ethyl ketone, fatty acid esters such as ethyl acetate, butyl acetate, ethyl butyrate, and ethyl formate, diethyl ether, dipropyl Ethers such as ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4 Diols such as 3-pentanediol and 3-methyl-1,5-pentanediol , Alcohols having a linear or branched alkyl having 1 to 7 carbon atoms, alcohols such as cyclohexanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, polyethylene glycol, triethylene glycol monomethyl Ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 3-methoxybutyl acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, diethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl Glycol or glycol ethers such as ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, methyl-n-amyl Terpenes such as ketone, methyl ethyl ketone oxime, triacetin, γ-butyrolactone, 2-pyrrolidone, N-methylpyrrolidone, acetonitrile, N, N-dimethylformamide, N- (2-aminoethyl) piperazine, dimethyl sulfoxide, and terpineol It can be illustrated.
An organic solvent (c) may be used individually by 1 type, and 2 or more types may be mixed and used for it. It is possible to adjust the viscosity of the composition as appropriate using the organic solvent (c).
　中でも、沸点が高いため金属化合物（ａ）の熱分解反応時に蒸発して系から熱を奪う可能性が低く、また組成物中で各成分を良好に分散することができる点で、３-メトキシ-１-ブタノール、３-メトキシ-３-メチル-１-ブタノールのようなアルコキシ基を有するアルコール類、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類が好ましい。 Among them, 3-methoxy is low in that since it has a high boiling point, it is less likely to evaporate during the thermal decomposition reaction of the metal compound (a) and take heat away from the system, and each component can be well dispersed in the composition. Alcohols having an alkoxy group such as 1-butanol, 3-methoxy-3-methyl-1-butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol mono Glycol ethers such as ethyl ether and triethylene glycol monoethyl ether are preferred.
　また、組成物中の有機溶媒（ｃ）の含有量は、特に制限されないが、金属化合物（ａ）１重量部に対して、５重量部以上が好ましく、１０重量部以上がより好ましく、３０重量部以上がさらにより好ましい。この範囲であれば、組成物中の各成分を均一に混合できる。
　また、組成物中の有機溶媒（ｃ）の含有量は、金属化合物（ａ）１重量部に対して、１０００重量部以下が好ましく、５００重量部以下が好ましく、３００重量部以下が好ましい。この範囲であれば、反応液が希薄になりすぎて反応が長くなったり、回収コストが増大するという事態が避けられる。
　組成物中の有機溶媒（ｃ）の含有量としては、金属化合物（ａ）１重量部に対して、約５～１０００重量部、約５～５００重量部、約５～３００重量部、約１０～１０００重量部、約１０～５００重量部、約１０～３００重量部、約３０～１０００重量部約３０～５００重量部、約３０～３００重量部が挙げられる。 Further, the content of the organic solvent (c) in the composition is not particularly limited, but is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and 30 parts by weight with respect to 1 part by weight of the metal compound (a). Part or more is even more preferable. If it is this range, each component in a composition can be mixed uniformly.
Moreover, 1000 weight part or less is preferable with respect to 1 weight part of metal compounds (a), and, as for content of the organic solvent (c) in a composition, 500 weight part or less is preferable and 300 weight part or less is preferable. Within this range, it is possible to avoid situations where the reaction solution becomes too dilute and the reaction becomes longer or the recovery cost increases.
The content of the organic solvent (c) in the composition is about 5-1000 parts by weight, about 5-500 parts by weight, about 5-300 parts by weight, about 10 parts by weight with respect to 1 part by weight of the metal compound (a). -1000 parts by weight, about 10-500 parts by weight, about 10-300 parts by weight, about 30-1000 parts by weight, about 30-500 parts by weight, and about 30-300 parts by weight.
脂肪酸（ｄ）
　本発明の製造方法に用いる組成物には、必要に応じてさらに脂肪酸（ｄ）を添加してもよい。脂肪酸（ｄ）は、金属ナノ微粒子の表面に強く結合するため、導電性インク、又は導電性ペースト中における金属ナノ微粒子の分散性向上に寄与する。脂肪酸（ｄ）は、金属化合物（ａ）と結合する能力を有し、金属ナノ微粒子が生成した際に、金属ナノ微粒子の表面上で保護層として機能するものであれば、特に制限なく使用することができる。 Fatty acid (d)
Fatty acid (d) may be further added to the composition used in the production method of the present invention as necessary. Since the fatty acid (d) binds strongly to the surface of the metal nanoparticles, it contributes to the improvement of the dispersibility of the metal nanoparticles in the conductive ink or conductive paste. The fatty acid (d) is not particularly limited as long as it has an ability to bind to the metal compound (a) and functions as a protective layer on the surface of the metal nanoparticle when the metal nanoparticle is generated. be able to.
　脂肪酸（ｄ）の炭素数は、３以上１８以下のものであればよく、炭素数４以上１８以下のものが好ましい。
　脂肪酸（ｄ）としては、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸、２-エチルヘキサン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、α-リノレン酸等を例示することができる。また、シクロヘキサンカルボン酸のような環状アルキルカルボン酸も使用することができる。中でも、金属ナノ微粒子生成時の反応液中における分散安定性が良い点で、カプロン酸、２-エチルヘキシル酸、オレイン酸、リノール酸、α-リノレン酸が好ましい。
　脂肪酸（ｄ）は、１種を単独で、又は２種以上を混合して用いることができる。 The fatty acid (d) may have 3 to 18 carbon atoms, and preferably has 4 to 18 carbon atoms.
As the fatty acid (d), acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, An example is α-linolenic acid. Cyclic alkyl carboxylic acids such as cyclohexane carboxylic acid can also be used. Of these, caproic acid, 2-ethylhexylic acid, oleic acid, linoleic acid, and α-linolenic acid are preferred because of good dispersion stability in the reaction solution during the production of metal nanoparticles.
The fatty acid (d) can be used alone or in combination of two or more.
　組成物中の脂肪酸（ｄ）の含有量は、金属化合物（ａ）１重量部に対して、０．１重量部以上が好ましく、０．５重量部以上がより好ましく、１重量部以上がさらにより好ましい。この範囲であれば、金属ナノ微粒子の分散性向上効果が十分に得られる。
　また、組成物中の脂肪酸（ｄ）の含有量は、金属化合物（ａ）１重量部に対して、１５重量部以下が好ましく、１０重量部以下がより好ましく、８重量部以下がさらにより好ましい。一般に、脂肪酸（ｄ）は、金属ナノ微粒子と強く結合することが知られており、金属ナノ微粒子を用いた導電性インク、又は導電性ペーストを基板上に塗布した際に通常実施される熱処理では脱離し難く、組成物中に含まれる脂肪酸の多くが金属ナノ微粒子の表面に残留する傾向にあるが、上記範囲であれば、基板上の脂肪酸の残留が抑制される。
　金属化合物（ａ）１重量部に対する脂肪酸（ｄ）の含有量としては、約０．１重量部以上１５重量部以下、約０．５重量部以上１５重量部以下、約１重量部以上１５重量部以下、約０．１重量部以上１０重量部以下、約０．５重量部以上１０重量部以下、約１重量部以上１０重量部以下、約０．１重量部以上８重量部以下、約０．５重量部以上８重量部以下、約１重量部以上８重量部以下が挙げられる。 The content of the fatty acid (d) in the composition is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and further preferably 1 part by weight or more with respect to 1 part by weight of the metal compound (a). More preferred. If it is this range, the dispersibility improvement effect of a metal nanoparticle will be fully acquired.
The content of the fatty acid (d) in the composition is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, and still more preferably 8 parts by weight or less, relative to 1 part by weight of the metal compound (a). . In general, it is known that fatty acid (d) binds strongly to metal nanoparticles, and in a heat treatment usually performed when a conductive ink using metal nanoparticles or a conductive paste is applied on a substrate, Although it is hard to detach | leave, it exists in the tendency for many fatty acids contained in a composition to remain on the surface of a metal nanoparticle, but if it is the said range, the residue of the fatty acid on a board | substrate will be suppressed.
The content of the fatty acid (d) with respect to 1 part by weight of the metal compound (a) is about 0.1 part by weight to 15 parts by weight, about 0.5 part by weight to 15 parts by weight, about 1 part by weight to 15 parts by weight. Parts by weight, about 0.1 to 10 parts by weight, about 0.5 to 10 parts by weight, about 1 to 10 parts by weight, about 0.1 to 8 parts by weight, about 0.5 parts by weight or more and 8 parts by weight or less, and about 1 part by weight or more and 8 parts by weight or less are included.
　アミン化合物（ａ）と脂肪酸（ｄ）のモル比は、アミン化合物（ａ）：脂肪酸（ｄ）が、約９０：１０～約９９．９：０．１の範囲であればよく、約９５：５～約９９．９：０．１の範囲であることが好ましく、約９５：５～約９９．５：０．５の範囲であることが好ましい。上記範囲内であれば、金属ナノ粒子の分散性を十分に向上させることができる保護層であって、また金属ナノ粒子を含む導電性インク、又は導電性ペーストを基板上に塗布した際、比較的低温の熱処理によって金属ナノ微粒子表面から容易に脱離する保護層を形成できる。 The molar ratio of the amine compound (a) to the fatty acid (d) is such that the amine compound (a): fatty acid (d) is in the range of about 90:10 to about 99.9: 0.1, and about 95: It is preferably in the range of 5 to about 99.9: 0.1, and preferably in the range of about 95: 5 to about 99.5: 0.5. If it is within the above range, it is a protective layer that can sufficiently improve the dispersibility of the metal nanoparticles, and when the conductive ink containing the metal nanoparticles or the conductive paste is applied on the substrate, the comparison is made. A protective layer that is easily detached from the surface of the metal nanoparticle can be formed by heat treatment at a low temperature.
金属ナノ微粒子の製造方法
　上述した組成物を以下に例示する金属ナノ微粒子の製造方法に用いることで、平均粒子径約２０ｎｍ以上２００ｎｍ以下の範囲の金属ナノ微粒子を製造することができる。 Method for Producing Metal Nanoparticles By using the above-described composition in a method for producing metal nanoparticle exemplified below, metal nanoparticle having an average particle diameter of about 20 nm to 200 nm can be produced.
調整工程
　本発明の製造方法は、上記組成物の調整工程を含むことができるが、予め調整された上記組成物を使用することもできる。調整工程における各成分の混合方法、及び混合順序は、各成分が組成物中で均一に分散され、また混合された状態となる方法であれば、特に制限されない。混合方法として、メカニカルスターラー、マグネティックスターラー、ボルテックスミキサー、遊星ミル、ボールミル、三本ロール、ラインミキサー、プラネタリーミキサー、ディゾルバー等を用いる方法例示でき、製造設備の規模や能力に応じて、これらの方法から適宜選択して実施することができる。なお、混合時の溶解熱、摩擦熱等の影響で組成物の温度が上昇し、金属ナノ微粒子の熱分解反応が開始することを回避するたに、調整工程における混合は、組成物の温度が６０℃以下となるように行うことが好ましく、４０℃以下に抑えながら行うことがより好ましい。 Adjustment Process The production method of the present invention can include an adjustment process of the composition, but the composition prepared in advance can also be used. The mixing method and mixing order of each component in the adjusting step are not particularly limited as long as each component is uniformly dispersed in the composition and becomes a mixed state. Examples of mixing methods include mechanical stirrers, magnetic stirrers, vortex mixers, planetary mills, ball mills, three rolls, line mixers, planetary mixers, dissolvers, etc., and these methods can be used according to the scale and capacity of the production equipment. Can be selected as appropriate from the above. In order to avoid the temperature of the composition from rising due to the effects of heat of fusion, frictional heat, etc. during mixing and initiating the thermal decomposition reaction of the metal nanoparticles, It is preferable to carry out so that it may become 60 degrees C or less, and it is more preferable to carry out, suppressing to 40 degrees C or less.
反応工程
　上記説明した組成物を反応容器で熱反応（反応工程）に供することにより、金属化合物（ａ）の熱分解反応が起こり、金属ナノ微粒子が生成する。反応方法は、プリンテッドエレクトロニクスに供される金属ナノ微粒子の製造方法において通常行われる方法であれば、特に制限されない。例えば、予め加熱しておいた反応容器内に組成物を導入してもよく、組成物を反応容器内導入した後に加熱してもよい。 Reaction Step By subjecting the composition described above to a thermal reaction (reaction step) in a reaction vessel, a thermal decomposition reaction of the metal compound (a) occurs, and metal nanoparticles are generated. The reaction method is not particularly limited as long as it is a method usually performed in a method for producing metal nanoparticles used for printed electronics. For example, the composition may be introduced into a reaction vessel that has been heated in advance, or the composition may be heated after being introduced into the reaction vessel.
　本発明の反応工程における熱分解反応の反応温度としては、熱分解反応が進行し、金属ナノ粒子が生成する温度であればよく、５０℃以上であればよく、１００℃以上が好ましく、１２０℃以上がより好ましい。この範囲であれば、金属ナノ粒子が効率よく生成する。また、反応温度は、約２５０℃以下であればよく、２４０℃以下が好ましく、２３０℃以下がより好ましい。この範囲であれば、保護層構成成分の揮発が抑えられて、金属ナノ粒子表面に効率よく保護層を形成できる。
　反応温度としては、約５０℃以上２５０℃以下、約１００℃以上２５０℃以下、約１２０℃以上２５０℃以下、約５０℃以上２４０℃以下、約１００℃以上２４０℃以下、約１２０℃以上２４０℃以下、約５０℃以上２３０℃以下、約１００℃以上２３０℃以下、約１２０℃以上２３０℃以下が挙げられる。
　また、反応時間は、所望する平均粒子径の大きさや、それに応じた組成物の組成に合せて、適宜選択すればよい。例えば、約１分から１００時間であればよく、約１分から１０時間が好ましい。 The reaction temperature of the pyrolysis reaction in the reaction step of the present invention may be a temperature at which the pyrolysis reaction proceeds and metal nanoparticles are generated, may be 50 ° C. or more, preferably 100 ° C. or more, and preferably 120 ° C. The above is more preferable. If it is this range, a metal nanoparticle will produce | generate efficiently. Moreover, the reaction temperature should just be about 250 degrees C or less, 240 degrees C or less is preferable and 230 degrees C or less is more preferable. If it is this range, volatilization of a protective layer structural component will be suppressed and a protective layer can be efficiently formed in the metal nanoparticle surface.
The reaction temperature is about 50 ° C to 250 ° C, about 100 ° C to 250 ° C, about 120 ° C to 250 ° C, about 50 ° C to 240 ° C, about 100 ° C to 240 ° C, about 120 ° C to 240 ° C. Or less, about 50 to 230 ° C., about 100 to 230 ° C., about 120 to 230 ° C.
Further, the reaction time may be appropriately selected according to the desired average particle size and the composition of the composition corresponding thereto. For example, it may be about 1 minute to 100 hours, and preferably about 1 minute to 10 hours.
精製工程
　熱分解反応により生成した金属ナノ微粒子は、未反応原料（有機溶媒（ｃ）を添加した場合は、有機溶媒）を含む混合物として得られる。当該混合物を精製することによって、目的の金属ナノ微粒子を得ることができる。精製方法としては、通常のフィルターろ過による固液分離方法に加えて、金属ナノ微粒子と有機溶媒の比重差を利用した沈殿方法等を例示することができる。固液分離の具体的な方法として、遠心分離やサイクロン式、又はデカンタといった方法を例示することができる。これらの方法で精製を実施する際、金属ナノ微粒子を含有する混合物の粘度を調整するために、アセトン、メタノール等の低沸点溶媒で混合物を希釈してもよい。 The metal nanoparticle produced | generated by the refinement | purification process pyrolysis reaction is obtained as a mixture containing an unreacted raw material (an organic solvent when an organic solvent (c) is added). By purifying the mixture, the target metal nanoparticles can be obtained. Examples of the purification method include a precipitation method using the specific gravity difference between the metal nanoparticles and the organic solvent, in addition to a solid-liquid separation method by a normal filter filtration. As a specific method of solid-liquid separation, a method such as centrifugation, a cyclone method, or a decanter can be exemplified. When carrying out purification by these methods, the mixture may be diluted with a low-boiling solvent such as acetone or methanol in order to adjust the viscosity of the mixture containing metal nanoparticles.
　本発明の製造方法では、反応条件や反応に用いる組成物の組成を適時調整することにより、所望する平均粒子径の金属ナノ微粒子を得ることができる。例えば、平均粒子径は約２０ｎｍ以上２００ｎｍ以下の範囲、約２０ｎｍ以上１５０ｎｍ以下の範囲、約２０ｎｍ以上１００ｎｍ以下の範囲であり得る。
　本発明の製造方法によって得られる金属ナノ微粒子は、導電性インク、又は導電性ペーストに用いた際に、種々の溶媒に容易に分散することが可能である。さらには、本発明の製造方法によって得られる金属ナノ微粒子を用いて形成した回路は低い体積抵抗値を示すため、種々の導電材料等に用いることが可能である。 In the production method of the present invention, metal nanoparticles having a desired average particle size can be obtained by appropriately adjusting the reaction conditions and the composition of the composition used for the reaction. For example, the average particle size can be in the range of about 20 nm to 200 nm, in the range of about 20 nm to 150 nm, and in the range of about 20 nm to 100 nm.
The metal nanoparticles obtained by the production method of the present invention can be easily dispersed in various solvents when used in a conductive ink or conductive paste. Furthermore, since a circuit formed using metal nanoparticles obtained by the production method of the present invention exhibits a low volume resistance value, it can be used for various conductive materials.
　以下に、本発明を実施例により具体的に説明する。ただし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.
（１）材料
　実施例及び比較例の金属ナノ微粒子の製造に用いた組成物を構成する各成分を以下に示す。 (1) Each component which comprises the composition used for manufacture of the metal nanoparticle of a material Example and a comparative example is shown below.
金属化合物（ａ）
ａ１：蓚酸銀（（ＣＯＯＡｇ）２）
なお、蓚酸銀０．５モル（銀原子１モル）に対するアミン化合物（ｂ）のモル比を、０モルを超え、１モル以下の範囲で調整した。また、蓚酸銀は特許文献３（特開２０１２－１６２７６７）に記載の方法により合成した。 Metal compound (a)
a1: Silver oxalate ((COOAg) 2 )
In addition, the molar ratio of the amine compound (b) to 0.5 mol of silver oxalate (1 mol of silver atoms) was adjusted in the range of more than 0 mol and 1 mol or less. Silver oxalate was synthesized by the method described in Patent Document 3 (Japanese Patent Application Laid-Open No. 2012-162767).
アミン化合物（ｂ）
ｂ１：ｎ-ドデシルアミン（和光純薬工業株式会社製）
ｂ２：ｎ-オクチルアミン（和光純薬工業株式会社製）
ｂ３：Ｎ,Ｎ-ジメチル-１,３-プロパンジアミン（和光純薬工業株式会社製）
ｂ４：ｎ-ブチルアミン（和光純薬工業株式会社製）
　ｎ-ドデシルアミン、ｎ-オクチルアミン、Ｎ,Ｎ-ジメチル-１,３-ジアミノプロパン、ｎ-ブチルアミンを、それぞれ１０モル％、５０モル％、５モル％、３５モル％配合して、アミン化合物液（ｂ）混合液を調製し、全ての実施例及び比較例に用いた。なお、アミン化合物（ｂ）液と蓚酸銀中の銀原子（ａ１）のモル比（アミン化合物（ｂ）／銀原子（ａ１））は、後述する表１に示す比率に調整した。 Amine compound (b)
b1: n-dodecylamine (manufactured by Wako Pure Chemical Industries, Ltd.)
b2: n-octylamine (Wako Pure Chemical Industries, Ltd.)
b3: N, N-dimethyl-1,3-propanediamine (manufactured by Wako Pure Chemical Industries, Ltd.)
b4: n-butylamine (manufactured by Wako Pure Chemical Industries, Ltd.)
n-dodecylamine, n-octylamine, N, N-dimethyl-1,3-diaminopropane, and n-butylamine are compounded at 10 mol%, 50 mol%, 5 mol%, and 35 mol%, respectively, to form an amine compound The liquid (b) liquid mixture was prepared and used for all the Examples and Comparative Examples. In addition, the molar ratio (amine compound (b) / silver atom (a1)) of the amine compound (b) solution and the silver atom (a1) in the silver oxalate was adjusted to the ratio shown in Table 1 described later.
有機溶媒（ｃ）
ｃ１：３-メトキシ-３-メチル-１-ブタノール（東京化成工業株式会社製）
ｃ２：ジエチレングリコールモノブチルエーテル（和光純薬工業株式会社製） Organic solvent (c)
c1: 3-methoxy-3-methyl-1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
c2: Diethylene glycol monobutyl ether (Wako Pure Chemical Industries, Ltd.)
（２）金属ナノ微粒子の製造
　磁気撹拌子を入れた５０ｍＬガラス製遠沈管に、上記アミン化合物（ｂ）混合液を表１に示すモル量となる量（０．９ｇ（実施例３、５）、１．８ｇ（実施例１、２、４）、３．６ｇ（比較例１、２））を投入し、有機溶媒（ｃ）を添加する実施例においては、表１に示す重量（１．５ｇ（実施例２、３、比較例２）、３．０ｇ（実施例４、５））を添加し、磁気攪拌機にて１分程度攪拌し、金属ナノ微粒子の製造（反応）に用いる各組成物を調整した。その後、表１に示すように、３．０ｇの硝酸銀（ａ１）を添加し、室温下で約１０分攪拌したのち、遠沈管を立てて設置可能なアルミブロックを備えたホットスターラー（小池精密機器製作所製ＨＨＥ-１９Ｇ-Ｕ）上にて１３０℃で加熱した。加熱開始から１０～１５分で反応が開始し、その後３分～１０分程度で反応が終了した。放冷後、磁気撹拌子を取り出し、メタノール３０ｇを添加してボルテックスミキサーで攪拌した後、遠心分離機（日立工機製ＣＦ７Ｄ２）にて３０００ｒｐｍ（約１６００×Ｇ）、１分間遠沈操作を実施し、上澄みを除去した。メタノール添加、撹拌、遠心分離、及び上澄み除去の工程を２回繰り返し、製造された各金属ナノ微粒子を回収した。
　各実施例及び比較例で使用した組成物の組成を後掲の表１に示す。 (2) Production of metal nanoparticles In a 50 mL glass centrifuge tube containing a magnetic stirrer, the amine compound (b) mixed solution is in an amount (0.9 g (Examples 3 and 5)) in the molar amount shown in Table 1. 1.8 g (Examples 1, 2 and 4), 3.6 g (Comparative Examples 1 and 2)) and the organic solvent (c) is added, the weight (1. 5 g (Examples 2 and 3 and Comparative Example 2) and 3.0 g (Examples 4 and 5)) were added and stirred for about 1 minute with a magnetic stirrer, and each composition used for the production (reaction) of metal nanoparticles. I adjusted things. After that, as shown in Table 1, 3.0 g of silver nitrate (a1) was added, stirred for about 10 minutes at room temperature, and then a hot stirrer equipped with an aluminum block that could be installed with a centrifuge tube (Koike Precision Equipment) It heated at 130 degreeC on the manufacturing company make HHE-19G-U). The reaction started in 10 to 15 minutes from the start of heating, and then finished in about 3 to 10 minutes. After cooling, the magnetic stirrer is taken out, 30 g of methanol is added and the mixture is stirred with a vortex mixer, and then centrifuged at 3000 rpm (about 1600 × G) for 1 minute with a centrifuge (CF7D2 manufactured by Hitachi Koki). The supernatant was removed. The steps of adding methanol, stirring, centrifuging, and removing the supernatant were repeated twice to collect each produced metal nanoparticle.
The composition of the composition used in each example and comparative example is shown in Table 1 below.
（３）導電性インクの調製
　各反応で得られた金属ナノ微粒子は、遠沈管を傾けすべての溶媒を除去後、導電性インク化用溶媒（オクタン／ブタノール＝８０／２０（Ｖｏｌ／Ｖｏｌ％）を、風袋差引した金属ナノ微粒子重量と同重量投入し、銀ナノ微粒子を分散させることで導電性インクを調製した。 (3) Preparation of conductive ink The metal nanoparticles obtained in each reaction, after removing all the solvent by tilting the centrifuge tube, the solvent for converting to conductive ink (octane / butanol = 80/20 (Vol / Vol%)) Was charged in the same weight as the weight of the metal nanoparticles finely subtracted, and silver nanoparticles were dispersed to prepare a conductive ink.
（４）金属ナノ微粒子の平均粒子径の測定
　得られた銀ナノ粒子分散インクとスピンコーター（アクテス社製ＡＳＣ-４０００、１５００ｒｐｍ）を用い、ＰＥＴフィルム（東レ製ルミラーＵ４８３）上に４００ｎｍ厚さの薄膜を作製した。得られた金属薄膜を未焼成のまま走査型電子顕微鏡（日立ハイテク製Ｓ-４５００）で観察し、表面の粒子形状を観察した。平均粒子径は画像の粒子の長辺を計測し、２０個の粒子の平均値から算出した。結果を表１に示す。 (4) Measurement of average particle diameter of metal nanoparticles Using the obtained silver nanoparticle-dispersed ink and a spin coater (ASC-4000 manufactured by Actes Co., Ltd., 1500 rpm), a 400 nm thick film is formed on a PET film (Toray Lumirror U483). A thin film was prepared. The obtained metal thin film was observed with a scanning electron microscope (S-4500, manufactured by Hitachi High-Tech) without firing, and the particle shape of the surface was observed. The average particle diameter was calculated from the average value of 20 particles by measuring the long sides of the image particles. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001













（５）導電性の評価
　実施例１～５、及び比較例１、２の各導電性インクとスピンコーター（アクテス社製ＡＳＣ-４０００、１５００ｒｐｍ）を用い、ＰＥＴフィルム（東レ製ルミラーＵ４８３）上に４００ｎｍ厚さの薄膜を作製した。スピンコートによって得られた金属薄膜を室温下３日間放置したものの抵抗値（熱処理無）、及びスピンコート後速やかに７０℃にて１時間熱処理を施したものの抵抗値（熱処理有）を、それぞれ四探針型導電率計（三菱化学アナリテック製ロレスターＡＸ）を用いて測定した。結果を表２に示す。 (5) Conductivity evaluation Using the conductive inks of Examples 1 to 5 and Comparative Examples 1 and 2 and a spin coater (ASC-4000 manufactured by Actes Co., Ltd., 1500 rpm) on a PET film (Toray Lumirror U483). A thin film having a thickness of 400 nm was prepared. The resistance value (without heat treatment) of the metal thin film obtained by spin coating for 3 days at room temperature and the resistance value (with heat treatment) of heat treatment at 70 ° C. for 1 hour immediately after spin coating were measured. Measurement was performed using a probe-type conductivity meter (Lorestar AX manufactured by Mitsubishi Chemical Analytech). The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002











　実施例１は、（ｂ）／（ａ１）＝０．８として金属ナノ微粒子を作製した。得られた金属ナノ微粒子とそれを用いた導電性インクは暗い紺色であり、平均粒子径は７７．９ｎｍであった。 Example 1 produced metal nanoparticles with (b) / (a1) = 0.8. The obtained metal nanoparticles and the conductive ink using the same were dark amber and the average particle size was 77.9 nm.
　実施例２は、有機溶媒（ｃ）を添加した以外は、実施例１と同様とした。有機溶媒（ｃ）を添加した後、実施例１と比較して組成物中で金属化合物とアミン化合物がより均一に分散していた。得られた金属ナノ微粒子の平均粒子径は２３．５ｎｍであった。 Example 2 was the same as Example 1 except that the organic solvent (c) was added. After the organic solvent (c) was added, the metal compound and the amine compound were more uniformly dispersed in the composition as compared with Example 1. The average particle diameter of the obtained metal nanoparticles was 23.5 nm.
　実施例３は、（ｂ）／（ａ１）＝０．４とした以外は、実施例２と同様とした。実施例３においても組成物は均一に分散していたが、加熱開始から反応が開始されるまでの時間が実施例２よりもやや長かった。得られた金属ナノ微粒子の平均粒子径は６４．６ｎｍであった。 Example 3 was the same as Example 2 except that (b) / (a1) = 0.4. Also in Example 3, the composition was uniformly dispersed, but the time from the start of heating to the start of the reaction was slightly longer than in Example 2. The average particle diameter of the obtained metal nanoparticles was 64.6 nm.
　実施例４は、（ｂ）／（ａ１）＝０．４、有機溶媒（ｃ）の添加量を２倍とした以外は、実施例２と同様とした。加熱開始から反応が開始されるまでの時間は、実施例２及び実施例３より長く、約１５分であった。得られた金属ナノ微粒子の平均粒子径は５３．７ｎｍであった。 Example 4 was the same as Example 2 except that (b) / (a1) = 0.4 and the amount of organic solvent (c) added was doubled. The time from the start of heating to the start of the reaction was longer than that of Example 2 and Example 3, and was about 15 minutes. The average particle diameter of the obtained metal nanoparticles was 53.7 nm.
　実施例５は、有機溶媒（ｃ）をジエチレングリコールモノブチルエーテルに変更した以外は、実施例２と同様とした。組成物は、実施例２～４と同じく均一に分散していた。また、加熱開始から反応が開始されるまでに約１０分を要した。得られた金属ナノ微粒子の平均粒子径は２８．８ｎｍであった。 Example 5 was the same as Example 2 except that the organic solvent (c) was changed to diethylene glycol monobutyl ether. The composition was uniformly dispersed as in Examples 2-4. In addition, it took about 10 minutes from the start of heating to the start of the reaction. The average particle diameter of the obtained metal nanoparticles was 28.8 nm.
　比較例１は、（ｂ）／（ａ１）＝１．６とした以外は実施例１と同様とした。得られた金属ナノ微粒子の平均粒子径は１６．４ｎｍであり、平均粒子径２０ｎｍ以上の金属ナノ微粒子は得られなかった。 Comparative Example 1 was the same as Example 1 except that (b) / (a1) = 1.6. The average particle diameter of the obtained metal nanoparticles was 16.4 nm, and metal nanoparticles having an average particle diameter of 20 nm or more were not obtained.
　比較例２は、（ｂ）／（ａ１）＝１．６とした以外は実施例２と同様とした。得られた金属ナノ微粒子の平均粒子径は１８．７ｎｍであり、平均粒子径２０ｎｍ以上の金属ナノ微粒子は得られなかった。 Comparative Example 2 was the same as Example 2 except that (b) / (a1) = 1.6. The average particle diameter of the obtained metal nanoparticles was 18.7 nm, and metal nanoparticles having an average particle diameter of 20 nm or more were not obtained.
　表２から、熱処理の有無によらず、金属ナノ微粒子の平均粒子径が大きいほど抵抗値が低い傾向であることが分かる。これは、室温放置および７０℃の熱処理では、温度が低いために金属ナノ微粒子の表面にアミン化合物（ｂ）の被覆が残存しており、粒子径の大きい、すなわち比表面積の小さい金属ナノ微粒子の方が、アミン化合物の残存量が少ないために抵抗値が低くなったためと考えられる。
　本発明の各実施例の金属ナノ粒子の導電性は、平均粒子径２０ｎｍ未満の比較例の金属ナノ粒子とほぼ同等以上の導電性を有していた。また、本発明の各実施例の金属ナノ粒子は、平均粒子径が比較的大きいために、保護層の量が比較的少なく、その分、金属ナノ粒子を含む導電性インク又はペーストの熱処理時間を短くし、又は熱処理温度を低くすることができる。即ち、本発明の金属ナノ粒子は、平均粒子径２０ｎｍ未満の金属ナノ粒子が有する高い導電性を保持しながら、導電性インク又はペーストの熱処理温度又は時間を小さくできるものである。 From Table 2, it can be seen that the resistance value tends to be lower as the average particle size of the metal nanoparticles is larger regardless of the presence or absence of heat treatment. This is because the coating of the amine compound (b) remains on the surface of the metal nanoparticle because the temperature is low at room temperature and heat treatment at 70 ° C., and the metal nanoparticle having a large particle diameter, that is, a specific surface area is small. However, it is considered that the resistance value was lowered because the remaining amount of the amine compound was small.
The conductivity of the metal nanoparticles of each example of the present invention was almost equal to or higher than the conductivity of the metal nanoparticles of the comparative example having an average particle diameter of less than 20 nm. In addition, since the metal nanoparticles of each example of the present invention have a relatively large average particle diameter, the amount of the protective layer is relatively small, and accordingly, the heat treatment time of the conductive ink or paste containing the metal nanoparticles is increased. It can be shortened or the heat treatment temperature can be lowered. That is, the metal nanoparticles of the present invention can reduce the heat treatment temperature or time of the conductive ink or paste while maintaining the high conductivity of the metal nanoparticles having an average particle diameter of less than 20 nm.
　本発明の製造方法で得られた金属ナノ微粒子を用いて調製した導電性インクは、短時間の熱処理で高い電気伝導性を発現するため、基材の耐熱性の制限を受けることなく、ガラス基板、ポリマーフィルムなど広範囲の基板に対する各種印刷方法に適用できる。具体的には、電気回路配線、電極形成に用いるプリンテッドエレクトロニクス向け材料として有効に利用することができる。本発明の製造方法で得られた金属ナノ微粒子は、さらには、導電性の接着剤、電磁波吸収体、光反射体等の各分野においても有効に利用することができる。 The conductive ink prepared by using the metal nanoparticles obtained by the production method of the present invention exhibits high electrical conductivity by a short heat treatment, and thus is not limited by the heat resistance of the base material. It can be applied to various printing methods for a wide range of substrates such as polymer films. Specifically, it can be effectively used as a material for printed electronics used for electric circuit wiring and electrode formation. Furthermore, the metal nanoparticles obtained by the production method of the present invention can be effectively used in various fields such as conductive adhesives, electromagnetic wave absorbers, and light reflectors.

Claims (12)

  1. 　金属化合物（ａ）とアミン化合物（ｂ）を含有する組成物を反応させる金属ナノ微粒子の製造方法であって、組成物中のアミン化合物（ｂ）の含有量が、金属化合物（ａ）に含まれる金属原子の物質量１ｍｏｌに対して、０ｍｏｌを超え１ｍｏｌ以下の範囲であることを特徴とする方法。 It is a manufacturing method of the metal nanoparticle which makes the composition containing a metal compound (a) and an amine compound (b) react, Comprising: Content of the amine compound (b) in a composition is contained in a metal compound (a) The method is characterized by being in the range of more than 0 mol and not more than 1 mol with respect to 1 mol of the metal atom.
  2. 　組成物が、さらに、２０℃の水に対して１ｇ／Ｌ以上溶解する有機溶媒（ｃ）を含有する請求項１に記載の製造方法。 The production method according to claim 1, wherein the composition further contains an organic solvent (c) that dissolves 1 g / L or more in water at 20 ° C.
  3. 　有機溶媒（ｃ）が、エーテル結合とヒドロキシル基を有する溶媒を含む請求項２に記載の製造方法。 The production method according to claim 2, wherein the organic solvent (c) contains a solvent having an ether bond and a hydroxyl group.
  4. 　有機溶媒（ｃ）が、グリコールエーテル類、及びアルコキシ基を有するアルコール類からなる群より選ばれる少なくとも１種の溶媒を含む請求項２又は３に記載の製造方法。 The production method according to claim 2 or 3, wherein the organic solvent (c) contains at least one solvent selected from the group consisting of glycol ethers and alcohols having an alkoxy group.
  5. 　金属化合物（ａ）が、蓚酸金属塩である請求項１～４のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 4, wherein the metal compound (a) is an oxalic acid metal salt.
  6. 　アミン化合物（ｂ）が、第１級アミン、及び第１級アミンと第３級アミンを有するジアミン化合物からなる群より選ばれる少なくとも１種である請求項１～５のいずれかに記載の製造方法。 6. The production method according to claim 1, wherein the amine compound (b) is at least one selected from the group consisting of a primary amine and a diamine compound having a primary amine and a tertiary amine. .
  7. 　組成物が、さらに、脂肪酸（ｄ）を含有する請求項１～６のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 6, wherein the composition further comprises a fatty acid (d).
  8. 　組成物中の脂肪酸の含有量が、金属化合物（ａ）１重量部に対して、０．１重量部以上１５重量部以下である請求項７に記載の製造方法。 The production method according to claim 7, wherein the content of the fatty acid in the composition is from 0.1 parts by weight to 15 parts by weight with respect to 1 part by weight of the metal compound (a).
  9. 　反応が、５０℃以上２５０℃以下の温度での熱分解反応である請求項１～８のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 8, wherein the reaction is a thermal decomposition reaction at a temperature of 50 ° C or higher and 250 ° C or lower.
  10. 　請求項１～９のいずれかに記載の製造方法により得られた平均粒子径が２０ｎｍ以上２００ｎｍ以下の金属ナノ微粒子。 Metal nanoparticles having an average particle size of 20 nm or more and 200 nm or less obtained by the production method according to any one of claims 1 to 9.
  11. 　請求項１～９のいずれかに記載の製造方法により得られた金属ナノ微粒子を含有する導電性インク組成物、又は導電性ペースト。 A conductive ink composition or a conductive paste containing metal nanoparticles obtained by the production method according to any one of claims 1 to 9.
  12. 　請求項１１に記載の導電性インク組成物、又は導電性ペーストを用いて形成された回路配線又は電極。 A circuit wiring or an electrode formed using the conductive ink composition according to claim 11 or a conductive paste.
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