WO2016204105A1 - Composition pour la fabrication de nanoparticules métalliques - Google Patents

Composition pour la fabrication de nanoparticules métalliques Download PDF

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WO2016204105A1
WO2016204105A1 PCT/JP2016/067485 JP2016067485W WO2016204105A1 WO 2016204105 A1 WO2016204105 A1 WO 2016204105A1 JP 2016067485 W JP2016067485 W JP 2016067485W WO 2016204105 A1 WO2016204105 A1 WO 2016204105A1
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metal nanoparticles
metal
composition
acid
oxalate
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PCT/JP2016/067485
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English (en)
Japanese (ja)
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謙輔 川村
崇充 森
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株式会社大阪ソーダ
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Priority to KR1020177030023A priority Critical patent/KR20180018485A/ko
Priority to CN201680028726.3A priority patent/CN107614164A/zh
Priority to JP2017525210A priority patent/JP6673352B2/ja
Publication of WO2016204105A1 publication Critical patent/WO2016204105A1/fr

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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
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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

Definitions

  • the present invention relates to a composition for producing metal nano-particles which are materials of conductive paste or ink used for wiring formation of electronic parts.
  • printed electronics which is a new circuit formation (patterning) method that replaces the conventional plating method and vapor deposition-photolithography method, and directly forms circuits by printing, has attracted attention as the next-generation industrial base. ing.
  • This technology uses a conductive paste or conductive ink to form a desired circuit pattern on a substrate. From basic circuit components such as thin film transistors, resistors, inductors, and capacitors, batteries, displays, sensors, RFID (Radio Frequency Identification), and many applications such as solar cells can be widely applied.
  • RFID Radio Frequency Identification
  • a conductive paste or ink containing nano-sized metal nanoparticles is promising.
  • the noble metal nanoparticles have high electrical conductivity, and the melting temperature is significantly lower than that of the bulk metal due to the nanosize effect resulting from the increase in surface energy.
  • nanoparticles with a small average particle size become unstable and easily aggregate due to an increase in surface energy. Therefore, they aggregate during the production of nanoparticles and after blending into various conductive inks or conductive pastes. Therefore, there is a problem that solid-liquid separation occurs.
  • the protective layer is required to be stably bonded to the metal nanoparticles in the conductive paste or ink to prevent the aggregation of the particles and to be easily detached from the surface of the metal nanoparticles by sintering at the time of circuit formation.
  • Patent Document 1 discloses coated metal nanoparticles obtained by heat-reacting a composition containing silver oxalate, an alkylamine having a boiling point of 100 to 250 ° C., and an alkyldiamine having a boiling point of 100 to 250 ° C. Teaches that they are less likely to agglomerate during storage and are easily desorbed by low temperature sintering (paragraph 0022).
  • Patent Document 2 discloses a coated metal nanoparticle obtained by reducing a metal salt insoluble in an alcohol solvent in the presence of a fatty acid having 8 or more carbon atoms and an aliphatic amine having 8 or more carbon atoms in an alcohol solvent.
  • the fine particles teach that there is little residual aliphatic amine on the surface of the fine particles after sintering (paragraph 0010).
  • metal salts include metal carbonates, hydroxides, sulfates, and the like (Examples).
  • Examples of fatty acids having 8 or more carbon atoms include oleic acid, octanoic acid, decanoic acid, dodecanoic acid, stearic acid and the like (paragraph 0030).
  • the protective layer of metal nanoparticles obtained by these methods is excellent in binding property to metal nanoparticles, but has a strong hydrophobicity, and therefore has a poor dispersibility in an ink or paste containing a polar solvent.
  • metal nanoparticles that are easily dispersed in a polar solvent are required so that the polymer can be selected from a wide range.
  • ink for inkjet uses a highly polar solvent, metal nanoparticles that are easily dispersed in a polar solvent are required.
  • Patent Document 3 heats a composition containing silver nitrate and oleylamine to obtain coated silver fine particles, and then heats the composition containing the coated silver fine particles and ricinoleic acid which is a kind of hydroxy acid.
  • a method for replacing the protective layer is disclosed (Example 4), which teaches that coated silver fine particles having good dispersibility in polar organic solvents such as texanol and terpineol can be obtained (paragraph 0007). ).
  • polar organic solvents such as texanol and terpineol
  • An object of the present invention is to provide a composition capable of obtaining metal nanoparticles that can be easily dispersed in a polar solvent or a solvent mixture having a high ratio of polar solvents by a heating reaction.
  • the present inventor has repeatedly researched and obtained metal nanoparticles obtained by heating and reacting a composition containing (A) a metal salt of oxalate, (B) an amine compound, and (C) a hydroxy fatty acid.
  • A a metal salt of oxalate
  • B an amine compound
  • C a hydroxy fatty acid
  • Item 1 A composition for producing metal nanoparticles comprising (A) a metal oxalate salt, (B) an amine compound, and (C) a hydroxy fatty acid.
  • Item 2. C) The composition according to item 1, wherein the hydroxy fatty acid is at least one selected from the group consisting of ricinoleic acid and 12-hydroxystearic acid.
  • Item 3. A) The composition of claim
  • the amine compound is one or more primary amines, one or more diamine compounds, or a combination of one or more primary amines and one or more diamine compounds.
  • Item 5. Item 5.
  • Item 9 The method according to Item 8, wherein the heating reaction temperature is 50 to 240 ° C.
  • Item 10. The method according to Item 8 or 9, wherein the metal nanoparticles have an average particle size of 10 to 200 nm.
  • Item 11. Item 11. A conductive ink or paste containing metal nanoparticles obtained by the method according to any one of Items 8 to 10.
  • Item 12. Item 8. A conductive ink or paste comprising a step of heating the composition according to any one of Items 1 to 7 to obtain metal nanoparticles, and a step of dispersing the metal nanoparticles in an organic solvent containing a polar organic solvent. Manufacturing method.
  • Item 13. Item 12. A circuit or electrode formed using the conductive ink or paste according to Item 11.
  • Item 15. Use of a composition comprising (A) a metal oxalate salt, (B) an amine compound, and (C) a hydroxy fatty acid for the production of metal nanoparticles.
  • Item 16 Use of (A) metal oxalate, (B) amine compound, and (C) hydroxy fatty acid in combination for the production of metal nanoparticles.
  • metal nanoparticles having excellent dispersibility in a polar solvent can be obtained.
  • the metal nanoparticles are excellent in dispersibility in a hydrophobic solvent that has been conventionally widely used as a material for conductive ink or paste.
  • the metal nano-particles are not easily detached from the protective layer in the conductive ink or paste, that is, they are excellent in storage stability.
  • composition for producing metal nanoparticles of the present invention comprises (A) a metal oxalate salt, (B) an amine compound, and (C) a hydroxy fatty acid.
  • Metal oxalate salts examples include gold oxalate, silver oxalate, copper oxalate, platinum oxalate, palladium oxalate, nickel oxalate, and aluminum oxalate.
  • silver oxalate and copper oxalate are preferable, and silver oxalate is more preferable in that metal nanoparticles having excellent conductivity can be efficiently generated by heating reaction.
  • Oxalic acid metal salts can be used singly or in combination of two or more.
  • the content of the metal oxalate salt in the composition is preferably 20% by weight or more, more preferably 25% by weight or more, and still more preferably 30% by weight or more based on the total amount of the composition. If it is this range, a metal nanoparticle will produce
  • the content of the metal oxalate salt in the composition is 20 to 70% by weight, 20 to 65% by weight, 20 to 60% by weight, 25 to 70% by weight, 25 to 65% by weight with respect to the total amount of the composition. %, 25 to 60% by weight, 30 to 70% by weight, 30 to 65% by weight, 30 to 60% by weight, and the like.
  • the amine compound can be used without limitation as long as it can bind to (A) the metal oxalate and can form a protective layer on the surface of the generated metal nanoparticles.
  • a primary amine (b-1) which is a compound in which one of the three hydrogen atoms of ammonia is substituted with a linear, branched, or cyclic hydrocarbon, two of which are substituted in the same manner.
  • Examples thereof include a tertiary amine (b-2) and a tertiary amine (b-3) in which three are similarly substituted.
  • (A) the ability to bind to the metal oxalate is high, and after applying the conductive ink or paste using the obtained metal nanoparticles on the substrate, the temperature is relatively low (for example, using a PET substrate).
  • the primary amine (b-1) is preferable in that it is easily detached from the surface of the metal nanoparticle by a heat treatment at a temperature of 120 ° C. or less).
  • Examples of the primary amine (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-hexadecy
  • cyclopropylamine, cyclobutylamine, cyclopropylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine which are alicyclic amines, aniline which is an aromatic amine, and the like can be exemplified.
  • ether amines such as 3-isopropoxypropylamine and isobutoxypropylamine can also be exemplified.
  • Secondary amines (b-2) include 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, N Examples include dialkyl monoamines such as -ethyl-N-propylamine and N-propyl-N-butylamine, and cyclic amines such as piperidine.
  • Tertiary amine (b-3) includes triethylamine, tributylamine, trihexylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dilaurylmonomethylamine 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-dibutyl-1,3-propanediamine, N, N-diisobutyl-1,3-propanediamine N, N′-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N′-diethyl-1,3-propanediamine, 1,4-butanediamine, N , N-dimethyl-1,4-butanediamine, N, N′-dimethyl-1,4
  • a diamine compound in which one of the amines is a primary amine and the other is a tertiary amine is excellent in the ability to bind to (A) metal oxalate and form metal nanoparticles. When it does, it is preferable at the point which forms a protective layer easily on the surface of a 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.
  • n-propylamine, isopropylamine, cyclohexane, and the like are stable in dispersion with metal nanoparticles in conductive ink or paste, and can be easily detached by low-temperature heat treatment during circuit formation.
  • Amine compounds can be used alone or in combination of two or more. Specifically, one or more of (b-1), (b-2), (b-3), (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 (B) amine compound in the composition is preferably 5% by weight or more, more preferably 10% by weight or more, and still more preferably 20% by weight or more based on the total amount of the composition. Within this range, it is possible to form a good bond with the metal oxalate and form a protective layer on the surface of the generated metal nanoparticles. Further, the content of the (B) amine compound in the composition is preferably 55% by weight or less, more preferably 50% by weight or less, and even more preferably 45% by weight or less based on the total amount of the composition. Within this range, it is possible to form a good bond with the metal oxalate and form a protective layer on the surface of the generated metal nanoparticles.
  • the content of the (B) amine compound in the composition is 5 to 55% by weight, 5 to 50% by weight, 5 to 45% by weight, 10 to 55% by weight, 10 to 50% with respect to the total amount of the composition.
  • Examples include ranges of 10% by weight, 10 to 45% by weight, 20 to 55% by weight, 20 to 50% by weight, 20 to 45% by weight, and the like.
  • the content of the (B) amine compound in the composition is preferably 0.4 mol or more, more preferably 0.6 mol or more, and even more preferably 1 mol or more with respect to 1 mol of the metal oxalate salt. Within this range, it is possible to form a good bond with the metal oxalate and form a protective layer on the surface of the generated metal nanoparticles.
  • the content of the (B) amine compound in the composition is preferably 10 mol or less, more preferably 8 mol or less, and even more preferably 6 mol or less with respect to 1 mol of the metal oxalate salt.
  • the amount of the (B) amine compound relative to 1 mol of the metal oxalate is 0.4 to 10 mol, 0.4 to 8 mol, 0.4 to 6 mol, 0.6 to 10 mol, 0.6 to 8 mol, 0.6
  • a range of ⁇ 6 mol, 1 ⁇ 10 mol, 1 ⁇ 8 mol, 1 ⁇ 6 mol and the like can be mentioned.
  • hydroxy fatty acid a compound having 3 to 24 carbon atoms and having one or more hydroxyl groups (for example, one) can be used.
  • hydroxy fatty acids include 2-hydroxydecanoic acid, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, 2-hydroxyoctadecanoic acid, 2-hydroxyeicosanoic acid, 2-hydroxydocosanoic acid, 2-hydroxytricosanoic acid, 2-hydroxytetracosanoic acid, 3-hydroxyhexanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, 3-hydroxyundecanoic acid, 3-hydroxydodecanoic acid, 3-hydroxytridecanoic acid, 3-hydroxytetradecanoic acid, 3-hydroxyhexadecanoic acid, 3-hydroxyheptadecanoic acid, 3-hydroxyoctadecanoic acid,
  • hydroxy fatty acids having 4 to 18 carbon atoms and having one hydroxyl group other than the ⁇ position (particularly the 12th position) are preferred, and ricinoleic acid and 12-hydroxystearic acid are more preferred.
  • a hydroxy fatty acid can be used individually by 1 type or in combination of 2 or more types.
  • the content of (C) hydroxy fatty acid in the composition is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and even more preferably 0.1% by weight or more based on the total amount of the composition. preferable. Within this range, metal nanoparticles having practically sufficient dispersibility in polar solvents can be obtained. Further, the content of hydroxy fatty acid in the composition is preferably 15% by weight or less, more preferably 10% by weight or less, and still more preferably 8% by weight or less based on the total amount of the composition. Within this range, metal nanoparticles having practically sufficient dispersibility in polar solvents can be obtained.
  • the content of hydroxy fatty acid in the composition is 0.01 to 15% by weight, 0.01 to 10% by weight, 0.01 to 8% by weight, 0.05 to 15% by weight with respect to the total amount of the composition. %, 0.05 to 10% by weight, 0.05 to 8% by weight, 0.1 to 15% by weight, 0.1 to 10% by weight, 0.1 to 8% by weight, and the like.
  • the content of (C) hydroxy fatty acid in the composition is preferably 0.001 mol or more, more preferably 0.005 mol or more, and still more preferably 0.01 mol or more with respect to 1 mol of the metal oxalate salt.
  • metal nanoparticles having practically sufficient dispersibility in polar solvents can be obtained.
  • 1 mol or less is preferable with respect to 1 mol of oxalic acid metal salts, as for content of the hydroxy fatty acid in a composition, 0.5 mol or less is more preferable, and 0.25 mol or less is further more preferable.
  • metal nanoparticles having practically sufficient dispersibility in polar solvents can be obtained.
  • the amount of the hydroxy fatty acid relative to 1 mol of the metal oxalate is 0.001 to 1 mol, 0.001 to 0.5 mol, 0.001 to 0.25 mol, 0.005 to 1 mol, 0.005 to 0.5 mol, Examples thereof include 0.005 to 0.25 mol, 0.01 to 1 mol, 0.01 to 0.5 mol, 0.01 to 0.25 mol, and the like.
  • Organic solvent (S) The composition of the present invention may contain an organic solvent.
  • the organic solvent is preferably one that dissolves about 1 g / L or more in water at 20 ° C., and more preferably one that dissolves about 10 g / L or more.
  • the compound which has an ether bond and a hydroxyl group can be used conveniently as an organic solvent.
  • organic solvent 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 ether, and diethyl ether.
  • 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 ether
  • diethyl ether dipropyl ether
  • Ethers such as butyl 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-pentanediol , 3-Methyl-1,5-pentanedioe Diols such as, alcohols having a linear or branched alkyl having 1 to 7 carbon atoms, cyclohexanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 2- (2-eth
  • 2- (2-ethylhexyloxy) ethanol, 3-methoxy-1-butanol, 3-methoxy-3 are easy to handle because of their high boiling point, and each component can be well dispersed in the composition.
  • -Alcohols having an alkoxy group such as methyl-1-butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, etc.
  • the glycol ethers are preferred.
  • the content of the organic solvent in the composition is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and further preferably 30 parts by weight or more with respect to 100 parts by weight of the metal oxalate salt. More preferred. If it is this range, each component in a composition can be mixed uniformly.
  • the content of the organic solvent in the composition is preferably 1000 parts by weight or less, preferably 500 parts by weight or less, and preferably 300 parts by weight or less with respect to 100 parts by weight of the metal oxalate salt. 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 in the composition is 5 to 1000 parts by weight, 5 to 500 parts by weight, 5 to 300 parts by weight, 10 to 1000 parts by weight, 10 to 500 parts by weight with respect to 100 parts by weight of the metal oxalate salt. Parts by weight, 10 to 300 parts by weight, 30 to 1000 parts by weight, 30 to 500 parts by weight, 30 to 300 parts by weight, and the like.
  • the composition of this invention can contain the 1 type (s) or 2 or more types of additive used for the composition for metal fine particle manufacture applied to printed electronics in the range which does not affect the effect of this invention.
  • additives include fatty acids (fatty acids having 3 to 18 carbon atoms, such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid.
  • the composition of the present invention can be prepared by mixing each component. Mixing can be performed by a general-purpose apparatus such as a mechanical stirrer, a magnetic stirrer, a vortex mixer, a planetary mill, a ball mill, a triple roll, a line mixer, a planetary mixer, and a dissolver.
  • a general-purpose apparatus such as a mechanical stirrer, a magnetic stirrer, a vortex mixer, a planetary mill, a ball mill, a triple roll, a line mixer, a planetary mixer, and a dissolver.
  • the temperature of the composition is, for example, 60 ° C. or less, particularly 40 ° C. It is preferable to mix while keeping the temperature below °C.
  • the reaction temperature may be a temperature at which the thermal decomposition reaction proceeds and metal nanoparticles are generated. Examples thereof include 50 ° C. or higher, preferably 100 ° C. or higher, and more preferably 120 ° C. or higher. If it is this range, a metal nanoparticle will produce
  • Reaction temperatures include 50 to 250 ° C., 100 to 250 ° C., 120 to 250 ° C., 50 to 240 ° C., 100 to 240 ° C., 120 to 240 ° C., 50 to 200 ° C., 100 to 200 ° C., 120 to 200 ° C., etc. Is mentioned.
  • the said temperature is the temperature of the reaction liquid at the time of a heating reaction start.
  • the reaction time may be appropriately selected according to the desired average particle size and the composition of the composition corresponding thereto. Examples of the reaction time include 1 minute to 100 hours, preferably 1 minute to 10 hours.
  • purification process pyrolysis reaction is obtained as a mixture containing an unreacted raw material, it is preferable to refine
  • the purification method include a solid-liquid separation method and a precipitation method using a difference in specific gravity between the metal nanoparticle and an unreacted raw material such as an organic solvent.
  • the solid-liquid separation method include filter filtration, centrifugal separation, cyclone type, and decanter methods.
  • the viscosity of the mixture may be adjusted by diluting a mixture containing metal nanoparticles with a low-boiling solvent such as acetone or methanol.
  • the particle size metal nanoparticles composition for the preparation of metal nanoparticles By adjusting the composition and reaction conditions the particle size metal nanoparticles composition for the preparation of metal nanoparticles, it is possible to adjust the average particle size of the resulting metal nanoparticles.
  • metal nanoparticles having an average particle diameter of 10 to 200 nm, particularly 10 to 150 nm, particularly 10 to 100 nm, and particularly 10 to 50 nm can be obtained.
  • the average particle diameter is an average value of the lengths of the long sides of 20 fine particles in an image observed with a scanning electron microscope.
  • Conductive ink or paste contains metal nanoparticles obtained by the production method of the present invention described above and an organic solvent containing a polar organic solvent.
  • Organic solvents can include non-polar or hydrophobic solvents in addition to polar organic solvents.
  • polar organic solvents examples include ketones such as acetone, acetylacetone and methyl ethyl ketone; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran and 1,4-dioxane; 1,2-propanediol, 1,2-butane Diol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-pentanediol, 1,5-pentanediol Diols such as 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol Gly
  • linear or branched alcohols having 3 to 5 carbon atoms 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, and terpineol are preferable.
  • Nonpolar solvents include straight-chain, branched, or cyclic saturated hydrocarbons such as hexane, heptane, octane, nonane, decane, 2-ethylhexane, and cyclohexane; straight-chain or branched alcohols having 6 or more carbon atoms, etc. Alcohols such as benzene, toluene and benzonitrile; halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; methyl-n-amyl ketone; methyl ethyl ketone oxime; and triacetin.
  • straight-chain, branched, or cyclic saturated hydrocarbons such as hexane, heptane, octane, nonane, decane, 2-ethylhexane, and cyclohexane
  • Alcohols such as benzene, toluene and benzonit
  • saturated hydrocarbons and linear or branched alcohols having 6 or more carbon atoms are preferable, and hexane, octane, decane, octanol, decanol, and dodecanol are more preferable.
  • a solvent can be used individually by 1 type or in mixture of 2 or more types.
  • the ratio of the polar solvent is preferably 5% by volume or more, more preferably 10% by volume or more, and even more preferably 15% by volume or more based on the total amount of the solvent. Moreover, it can be 60 volume% or less, can also be 55 volume% or less, and can also be 50 volume% or less.
  • the solvent can also consist of a polar solvent. Even when the conductive ink or paste of the present invention contains a large amount of polar solvent, the dispersibility of the metal nanoparticles is good.
  • the conductive ink or paste of the present invention includes a heat or photocurable resin, a curing agent, a leveling agent, a thickening agent, a suspending agent, and a coupling agent for improving adhesion, which are usually included in the conductive ink or paste.
  • a heat or photocurable resin e.g., a heat or photocurable resin
  • a curing agent e.g., a curing agent
  • a leveling agent e.g., a leveling agent
  • a thickening agent e.g., a suspending agent
  • a coupling agent for improving adhesion which are usually included in the conductive ink or paste.
  • 1 type, or 2 or more types such as an antifoamer, a filler, a pH adjuster, a film formation adjuvant, and a water repellent.
  • an ink jet printing method, a screen printing method, a letterpress reverse printing method, a gravure are formed on a substrate.
  • a pattern to be a circuit or an electrode may be printed by a method such as an offset printing method, an offset printing method, a spin coating method, a spray coating method, a bar coating method, a die coating method, a slit coating method, a roll coating method, or a dip coating method. .
  • a temperature of 50 ° C. or higher preferably 80 ° C. or higher, more preferably 100 ° C. or higher, for example 200 ° C.
  • Firing can be performed using an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, flash lamp irradiation, microwaves, or the like.
  • Metal salt (A) a1 Silver oxalate ((COOAg) 2 ) Silver oxalate was synthesized by the method described in Patent Document 1 (Japanese Patent No. 5574761). a2: Silver nitrate (Wako Pure Chemical Industries, Ltd.)
  • fatty acid c1 ricinoleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • c2 12-hydroxystearic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • c3 Oleic acid (Wako Pure Chemical Industries, Ltd.)
  • Organic solvent (S) s1 2- (2-ethylhexyloxy) ethanol (manufactured by Wako Pure Chemical Industries, Ltd.)
  • s2 2-octanol (manufactured by Wako Pure Chemical Industries, Ltd.)
  • compositions having the compositions shown in Tables 1 and 2 below were prepared.
  • the amine compound (B) was mixed with other components after previously mixing a plurality of amine compounds.
  • Metal nanoparticles were prepared using silver nitrate (a2) as a raw material by the method described in Japanese Patent No. 5441550. Specifically, each component was mixed so as to have the composition shown in Table 2 to prepare a solution in which silver nitrate was completely dissolved, and 100 mL of this solution was transferred to a container equipped with a refluxer, and a mechanical stirrer (Tokyo Rika Instruments Co., Ltd.). The temperature was raised while stirring (300 rpm) using Z-2200). The heating rate was 1.0 ° C./min up to 120 ° C., and 0.5 ° C./min up to 120 ° C. up to 140 ° C.
  • the reaction was made to react at 140 degreeC for 1 hour, maintaining the said stirring state.
  • the reaction was performed while supplying nitrogen gas to the gas phase part of the container at a flow rate of 5 mL / min.
  • the reaction mixture was cooled to room temperature, and the slurry after the reaction was allowed to stand for 3 days, and then the supernatant was removed by decantation. At that time, the removal amount of the supernatant was adjusted so that the reduced silver was 20% by mass with respect to the total slurry.
  • Each metal nanoparticle obtained by removing the solvent is added to a dispersion solvent (2-propanol) so that the final concentration of the metal nanoparticle is 1% by weight and dispersed by dispersing the metal nanoparticle.
  • An ink for property evaluation was obtained.
  • each metal nanoparticle is introduced into a dispersion solvent (2-propanol) so that the final concentration of the metal nanoparticle is 50% by weight, and the metal nanoparticle is dispersed to conduct conductivity evaluation and SEM observation. Ink for average particle size evaluation was obtained.
  • the metal nanoparticles of Example 1 and Comparative Example 4 were dried under reduced pressure for 1 hour to prepare a sample for Tg measurement, and this sample was subjected to Tg measurement.
  • composition of the composition used in each example is shown in Table 1, and the composition of the composition used in each comparative example is shown in Table 2.
  • Example 1 ricinoleic acid was used as the hydroxy fatty acid.
  • Example 2 compared with Example 1, the ratio which occupies for the whole protective layer was increased. Further, n-octylamine and N, N-dimethyl-1,3-propanediamine were used as amine compounds.
  • Example 3 N, N-dimethyl-1,3-propanediamine used in Example 1 was not used as the amine compound, but 3-methoxypropylamine was used. As a result, the same tendency as in Examples 1 and 2 was observed in both dispersibility and conductivity.
  • Comparative Example 4 a metal salt other than silver oxalate was used. That is, in Comparative Example 4, metal nanoparticles were prepared using silver nitrate. As a result, all the metal nanoparticles had good dispersibility evaluation results in DLS, but sufficient conductivity was not obtained by firing at 100 ° C. for 1 hour.
  • the Tg measurement results shown in FIG. 1 are different in the conductivity of the obtained silver particles due to the change in weight at low temperature, that is, the difference in detachability during low-temperature sintering of the protective layer on the surface of the metal nanoparticles. Indicates that That is, FIG. 1 means that in the metal nanoparticle from which the protective layer is released at a lower temperature, the metal nanoparticle is sintered under mild firing conditions, and high conductivity is obtained.
  • the metal nanoparticles produced using the composition for producing metal nanoparticles of the present invention have good dispersibility in a conductive ink or paste containing a large amount of a polar solvent, it can be used for a wide range of applications.

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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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Abstract

Selon la présente invention, des nanoparticules métalliques sont obtenues par l'opération consistant à soumettre une composition pour la fabrication de nanoparticules métalliques à une réaction thermique, la composition comprenant (A) un oxalate métallique, (B) un composé amine et (C) un hydroxyacide gras. Les nanoparticules métalliques sont aisément dispersées dans un solvant polaire ou un mélange de solvants ayant une forte proportion d'un solvant polaire.
PCT/JP2016/067485 2015-06-15 2016-06-13 Composition pour la fabrication de nanoparticules métalliques WO2016204105A1 (fr)

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CN201680028726.3A CN107614164A (zh) 2015-06-15 2016-06-13 金属纳米微粒制造用组合物
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JP2018154806A (ja) * 2017-03-15 2018-10-04 Dic株式会社 金属微粒子分散体、導電性インク、および電子デバイス
WO2018180048A1 (fr) * 2017-03-29 2018-10-04 住友金属鉱山株式会社 Pâte électroconductrice
JP2019070076A (ja) * 2017-10-10 2019-05-09 Dic株式会社 オフセット印刷用金属微粒子インク
JP2019108593A (ja) * 2017-12-19 2019-07-04 Dic株式会社 銀微粒子分散体の製造方法
WO2022176809A1 (fr) * 2021-02-18 2022-08-25 学校法人 関西大学 Adhésif électroconducteur, corps fritté d'adhésif électroconducteur, procédé de production de corps fritté, composant électronique et procédé de production de composant électronique

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JP2018154806A (ja) * 2017-03-15 2018-10-04 Dic株式会社 金属微粒子分散体、導電性インク、および電子デバイス
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JP2019108593A (ja) * 2017-12-19 2019-07-04 Dic株式会社 銀微粒子分散体の製造方法
WO2022176809A1 (fr) * 2021-02-18 2022-08-25 学校法人 関西大学 Adhésif électroconducteur, corps fritté d'adhésif électroconducteur, procédé de production de corps fritté, composant électronique et procédé de production de composant électronique

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JP6673352B2 (ja) 2020-03-25
JPWO2016204105A1 (ja) 2018-03-29

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