WO2016039189A1 - Composite comprenant une composition de fines particules métalliques revêtues - Google Patents

Composite comprenant une composition de fines particules métalliques revêtues Download PDF

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WO2016039189A1
WO2016039189A1 PCT/JP2015/074566 JP2015074566W WO2016039189A1 WO 2016039189 A1 WO2016039189 A1 WO 2016039189A1 JP 2015074566 W JP2015074566 W JP 2015074566W WO 2016039189 A1 WO2016039189 A1 WO 2016039189A1
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ink
metal
capsule
encapsulated
encapsulated metal
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PCT/JP2015/074566
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English (en)
Japanese (ja)
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亮介 三井
中島　伸一郎
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日本航空電子工業株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C09D11/52—Electrically conductive inks
    • 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
    • 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 composite containing a composition of coated metal fine particles. More specifically, the present invention is a composite comprising a composition of coated metal fine particles, which breaks capsules by applying stimuli such as pressure, light, heat, pH change, UV irradiation, voltage, chemical reaction, etc.
  • the present invention relates to an encapsulated metal nanoink capable of forming a conductive thin film, and a dispersion of the encapsulated metal nanoink.
  • a film-like polymer material such as a flexible printed wiring board and a metal layer
  • the method for forming a metal layer on a film-like polymer material is limited to vapor deposition, sputtering, CVD, or plating using a toxic chemical that requires a vacuum environment, and a metal is easily formed on a substrate. It is difficult to form a layer.
  • conductive ink used for printing has metal particles dispersed in water or an organic solvent.
  • ink called nano ink has conductive metal nanoparticles coated with a protective agent dispersed therein. ing.
  • the protective agent is detached from the metal nanoparticles, whereby the metal nanoparticles are mutually fused and a conductive metal layer is formed.
  • the energy supply method include heat treatment (Non-Patent Document 1), microwave irradiation (Non-Patent Document 2), laser irradiation (Non-Patent Document 3), voltage application (Non-Patent Document 4), and the like.
  • Patent Document 1 In order to form a metal layer having practically sufficient conductivity, heat treatment at a high temperature of 200 ° C. or higher is required (Patent Document 1), and a polymer material having excellent workability and excellent heat resistance is required. There is a problem that the substrate is limited to polyimide.
  • Patent Document 2 a coating film on which ink composed of metal nanoparticles is printed is immersed in a polar solvent or a polar solvent solution containing a solubilizing agent, and the protective agent on the surface of the metal nanoparticles is removed in the solvent. Then, a method for obtaining a highly conductive thin film by drying the thin film at room temperature is disclosed.
  • Non-Patent Document 5 discloses that a protective film is removed by bringing a sodium chloride aqueous solution into contact with a thin film on which ink made of metal nanoparticles is printed, and then the thin film is dried at room temperature, thereby achieving high conductivity. A method for obtaining a conductive thin film is disclosed.
  • Patent Document 3 an ink made of metal nanoparticles is brought into contact with a receiving layer containing a porous inorganic filler, and the filler adsorbs a protective agent together with the solvent of the ink, thereby forming a highly conductive thin film.
  • a method of obtaining is disclosed.
  • Patent Document 2 and Non-Patent Document 5 can surely obtain a highly conductive thin film at room temperature, the effect is exhibited by bringing the treatment solution into contact with the printed ink. Therefore, depending on the purity of the solution used for the treatment and the degree of cleaning after the treatment, impurities may remain or unnecessary reactions may be induced, so that the conductivity of the thin film may not be sufficiently ensured.
  • Patent Documents 4 and 5 a protective agent is coordinately bonded to metal nanoparticles with a relatively weak force to produce an ink dispersed in a solvent, and dried at room temperature after printing the ink. It has been found that the protective agent can be detached by evaporation of the solvent alone, and the metal nanoparticles spontaneously adhere to each other to form a highly conductive thin film.
  • conductive inks for printed wiring conductive metal particles coated with a protective agent are dispersed in water or an organic solvent.
  • patterns printed using nano inks are protected from metal nanoparticles.
  • mutual fusion of the metal nanoparticles proceeds, and a conductive metal layer is formed.
  • the protective agent from the metal nanoparticles can be easily obtained along with evaporation of the solvent of the metal nano ink. Since the detachment of the metal nano ink occurs, it is necessary to store the metal nano ink in a sealed state, which is difficult to handle.
  • the conventional metal nano-ink is a low-temperature sinterability side effect and an effect resulting from poor storage stability. Since the agglomeration progresses, it was not possible to sinter at any timing after coating on the substrate. That is, the conventional metal nano-ink has no on-demand property (in the present invention, “has a property that a conductive film can be formed at a desired timing while having long-term storage stability”).
  • an object of the present invention is to provide a metal nano ink having on-demand properties.
  • the inventors of the present invention applied an ink composition containing metal nanoparticles coated with a protective agent to pressure, light, heat, pH change, UV irradiation, voltage, chemical
  • an ink composition containing metal nanoparticles coated with a protective agent to pressure, light, heat, pH change, UV irradiation, voltage, chemical
  • a stimulus such as a reaction
  • the storage stability of the ink composition is increased, and when the capsule is broken by giving such a stimulus, the ink contained in the capsule
  • the release of the chemical process derived from the composition induces mutual fusion of the metal nanoparticles and can form a conductive thin film at a low temperature.
  • the present invention includes the following (1) to (14).
  • An encapsulated metal nanoink having a plurality of metal nanoparticles coated with a protective agent inside the capsule, and capable of forming a conductive thin film by breaking the capsule with an external stimulus.
  • the protective agent is an amphiphilic molecule, the metal nanoparticles are dispersed in a hydrophobic organic solvent, and the capsule is composed of a hydrophilic compound derivative, as described in (1) or (2) above Encapsulated metal nano ink.
  • the metal nanoparticles are nanoparticles of at least one metal selected from the group consisting of gold, silver, copper, platinum, palladium, nickel, indium, rhodium and cobalt.
  • the hydrophobic organic solvent is at least one selected from the group consisting of n-hexane, n-heptane, n-octane, benzene and toluene.
  • the amphiphilic molecule is an aliphatic amine, sorbitan fatty acid ester, polyglycerin fatty acid ester, mercaptan, phosphate ester, aliphatic phosphate, alkylamine fatty acid salt, polypropylene oxide fatty acid ether, thiol and succinic acid derivative. 10.
  • the hydrophilic organic solvent is at least one selected from the group consisting of water-soluble alcohols, alkyl ethers derived from water-soluble alcohols, and alkyl esters of water-soluble alcohols. A dispersion of the encapsulated metal nanoink as described.
  • a metal nano ink having on-demand properties can be provided.
  • FIG. 1 is a schematic diagram showing an embodiment of the present invention.
  • FIG. 2 is an image showing an encapsulated metal nano ink in which the metal nano ink is encapsulated.
  • FIG. 3 is an image showing a thin film obtained by applying a load to the encapsulated metal nanoink prepared in Example 1 to crush the capsule and dry it at room temperature.
  • the location where the image of FIG. 4 is a scanning electron microscope (SEM) image obtained by photographing the edge portion of the thin film of FIG. 3 (observed with an acceleration voltage of 5 kV using JSM-6301F manufactured by JEOL Ltd.). The area where the image is taken is shown enclosed in a rectangle.
  • SEM scanning electron microscope
  • FIG. 5 is an SEM image obtained by photographing the conductive film when the capsule of the encapsulated metal nano-ink was crushed and dried at room temperature for 24 hours in Example 1 (using JSM-6301F manufactured by JEOL Ltd., Observed at an acceleration voltage of 5 kV).
  • FIG. 5 is an SEM image obtained by photographing the conductive film when the capsule of the encapsulated metal nano-ink was crushed and dried at room temperature for 24 hours in Example 1 (using JSM-6301F manufactured by JEOL Ltd., Observed at an acceleration voltage of 5 kV).
  • FIG. 6 is an SEM image obtained by photographing the conductive film when the encapsulated metal nano ink was left on the substrate at room temperature for 24 hours in Example 1 and the capsules were crushed and then dried at room temperature for 24 hours (Japan). Observation with an acceleration voltage of 5 kV using JSM-6301F manufactured by Denshi Co.).
  • FIG. 7 is an SEM image obtained by photographing the conductive film when the capsule of the encapsulated metal nanoink was crushed and dried at room temperature for 24 hours in Example 2 (using JSM-6301F manufactured by JEOL Ltd.). Observed at an acceleration voltage of 5 kV).
  • FIG. 7 is an SEM image obtained by photographing the conductive film when the capsule of the encapsulated metal nanoink was crushed and dried at room temperature for 24 hours in Example 2 (using JSM-6301F manufactured by JEOL Ltd.). Observed at an acceleration voltage of 5 kV).
  • FIG. 8 is an SEM image obtained by photographing the conductive film when the metal nano ink prepared in Example 1 was spin coated on the substrate and dried at room temperature for 24 hours in Comparative Example 1 (JSM-manufactured by JEOL Ltd.). (Observed with an acceleration voltage of 5 kV using 6301F).
  • FIG. 9 is an SEM image obtained by photographing the conductive film when the metal nano ink prepared in Example 2 was spin-coated on a substrate and dried at room temperature for 24 hours in Comparative Example 2 (JSM-manufactured by JEOL Ltd.). (Observed with an acceleration voltage of 5 kV using 6301F).
  • the characteristic features of the encapsulated metal nano-ink of the present invention compared to the prior art are that it has a plurality of metal nanoparticles coated with a protective agent in the capsule, and that the capsule is broken by an external stimulus to make it conductive. A thin film can be formed.
  • Patent Document 6 describes a silver ink core component containing 60% by weight or more of silver nanoparticles dispersed in a silver carrier and a shell carrier. Co-electrospinning with a shell component containing a film-forming polymer to deposit core-shell fibers on a substrate, and silver nanoparticles are sintered to form a population of silver nanowires, and the average population of silver nanowires is 60 ⁇ m or more A method for producing silver nanowires exhibiting length is described.
  • the shell of the core-shell fiber described in Patent Document 6 is not intended to prevent evaporation of the solvent from the silver ink core component, but to form high-aspect-ratio silver nanowires when silver nanoparticles are sintered. belongs to. That is, in the core-shell fiber described in Patent Document 6, the silver nanoparticles are sintered in the shell to form silver nanowires, whereas in the encapsulated metal nanoink of the present invention, the capsules are external. The metal nanoparticle is sintered ⁇ aggregated) outside the capsule after being destroyed by the stimulation from the above, and the conductive film is formed.
  • the encapsulated metal nano-ink of the present invention is an encapsulated metal nano-ink having a plurality of metal nanoparticles coated with a protective agent inside the capsule, and can form a conductive thin film by breaking the capsule by external stimulus. Encapsulated metal nano ink.
  • the method for confirming that there are a plurality of capsules inside the capsule can be performed by observing the aggregation of the metal nanoparticles in the metal nano ink over time using a microscope. That is, the encapsulated liquid component is taken out by destroying the capsule, and the particles can be confirmed by observing the state before being completely sintered. Further, as shown in FIG. If metal particles having a large particle diameter produced by fusing metal nanoparticles can be observed, it can be presumed that a plurality of metal nanoparticles existed in the ink before sintering.
  • the following procedure is preferable.
  • the method for confirming that the nanoparticles are coated with the protective agent is that the nanoparticles cannot be made into a stable dispersion unless they are coated with the protective agent. If they are not coated with the protective agent, they are aggregated even in the dispersion. Therefore, if it is a dispersion of metal nanoparticles inside the capsule, it can be estimated that the metal nanoparticles are coated with a protective agent.
  • the fact that the metal nanoparticles are dispersed in the solvent indicates that the metal nano ink encapsulated in the capsule is diluted, and the UV-Vis spectrum of the obtained diluted solution is measured. The peak is in the range of 400 to 600 nm. It can also be confirmed by detecting.
  • the encapsulated metal nanoink is placed in a suitable organic solvent (this organic solvent may be hexane, octane, acetonitrile, etc., but is preferably the same as the solvent of the metal nanoink in the capsule).
  • the capsule is broken to dilute the metal nano ink contained in the capsule, the capsule residue and the diluted solution are separated by a method such as filtration, and the UV-Vis spectrum of the obtained diluted solution is measured. If a peak is recognized at 600 nm, it is considered that the plasmon absorption of the metal nanoparticles is observed, and it can be seen that the nanoparticles were dispersed in the ink.
  • the encapsulated metal nano ink 100 of the present invention comprises at least the metal nano ink 102 and the capsule wall 101.
  • the metal nano ink 102 is a low-temperature sintered ink composed of the metal nanoparticles 105, the protective agent 104, and the solvent 103, and the protective agent is detached from the metal nanoparticles as the solvent evaporates in a room temperature environment. Is to give.
  • Metal nanoparticles The kind of the metal nanoparticles is not particularly limited, and examples thereof include nanoparticles of metal species such as gold, silver, copper, platinum, palladium, rhodium, ruthenium, iridium, and osmium. These metal species are used alone. Or two or more of them may be used in combination.
  • Metal nanoparticles can be obtained by various known methods such as laser ablation, chemical reduction, thermal decomposition of organometallic compounds, reduction of metal chlorides in the gas phase, and reduction of oxides in water. What was manufactured can be used. In the chemical reduction method, the metal nanoparticles are obtained by being stabilized with a protective agent and dispersed in a solvent. Therefore, it is particularly preferable to use metal nanoparticles synthesized by the chemical reduction method.
  • the average secondary particle diameter of the metal nanoparticles is not particularly limited, but is preferably in the range of 1 to 500 nm, more preferably in the range of 1 to 100 nm, still more preferably in the range of 1 to 50 nm, and still more preferably 1 Within the range of ⁇ 30 nm.
  • the average secondary particle diameter is a value measured by a dynamic light scattering method or a laser diffraction method.
  • the average secondary particle diameter of the metal nanoparticles in the metal nanoink encapsulated in the capsule is, for example, an appropriate organic solvent for the metal nanoink encapsulated in the capsule (this organic solvent may be hexane, octane, acetonitrile, etc. Is preferably the same as the solvent of the metal nano ink in the capsule.),
  • This organic solvent may be hexane, octane, acetonitrile, etc. Is preferably the same as the solvent of the metal nano ink in the capsule.
  • the capsule is broken in the solvent, the metal nano ink contained in the capsule is diluted, the capsule residue and the diluted solution are filtered, etc. It can also measure with the dynamic light scattering method or the laser diffraction method with respect to the diluted solution obtained by isolate
  • the protective agent is not particularly limited as long as it can ensure the dispersibility of the metal nanoparticles in a solvent.
  • the protective agent is an amphiphilic molecule ["hydrophilic group” that is compatible with water (aqueous phase) in one molecule. It is a generic term for molecules that have both “lipophilic groups” (hydrophobic groups) that are compatible with oil (organic phase). ].
  • HLB value of amphiphilic molecule [Hydrophile-Lipophile Balance: A value representing the degree of affinity of an amphiphilic molecule for water and oil (an organic compound insoluble in water).
  • the HLB value is small.
  • the HLB value is obtained by identifying the protective agent and using the Griffin method.
  • the protective agent can be identified by separating the metal nanoink encapsulated in the encapsulated metal nanoink and performing gas chromatography mass spectrometry (GC-MS) on the separated metal nanoink or a diluted solution thereof. it can.
  • GC-MS gas chromatography mass spectrometry
  • Amphiphilic molecules include the group consisting of alkylamines, sorbitan fatty acid esters, polyglycerol fatty acid esters, mercaptans, phosphate esters, aliphatic phosphates, alkylamine fatty acid salts, polypropylene oxide fatty acid ethers, thiols and succinic acid derivatives. At least one selected is preferred. Among these, alkylamine is preferable because of its low temperature sintering property and good dispersibility of nanoparticles in a solvent.
  • the alkylamine may be any of long-chain alkylamine, medium-chain alkylamine, and short-chain alkylamine, and may be used alone or in combination of two or more.
  • Examples of the long-chain alkylamine include oleylamine (C 18 H 37 N), and the medium-chain alkylamine (the alkyl group having 6 to 10 carbon atoms) includes octylamine. (C 8 H 19 N), hexylamine (C 6 H 15 N) and the like, and short chain alkylamines (alkyl group having 1 to 5 carbon atoms) include butylamine (C 4 H 11 N) and the like. Can be mentioned.
  • Hydrophobic organic solvents include n-octanol / water partition coefficient [chemical substances dissolved in two layers of organic solvent (n-octanol) and water and dissolved in each solution when in equilibrium. The ratio of quantities is called the distribution coefficient and is expressed as a logarithmic value. ] Is preferably 2 or more.
  • the n-octanol / water partition coefficient (Log 10 P OW ) is measured according to JIS Z 7260-117: 2006 “Partition coefficient (1-octanol / water) measurement test”.
  • hydrophobic organic solvent examples include aromatic hydrocarbons such as benzene, o-toluene, m-toluene, and p-toluene; aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane; diethyl ether, Hydrocarbon mixtures such as ligroin (JIS K 8937: 1994), petroleum benzine (JIS K 8534: 1996), petroleum ether (JIS K 8593: 2007);
  • the metal nanoink that can be used in the encapsulated metal nanoink of the present invention is preferably a low-temperature sinterable metal nanoink, and particularly preferably a room-temperature sinterable metal nanoink.
  • the low-temperature sinterable metal nano-ink is sintered by heat treatment at a temperature of less than 200 ° C., preferably 150 ° C. or less, more preferably 120 ° C. or less, still more preferably 100 ° C. or less, and even more preferably 50 ° C. or less.
  • the metal nano ink is capable of forming a metal film on a substrate.
  • the room temperature sinterable metal nano-ink is a metal nano-ink that can be sintered at a particularly low temperature among the low-temperature sinterable metal nano-inks, and is not heated or cooled without being subjected to heat treatment. It is a metal nano ink that can be sintered in a state) to form a metal film on a substrate.
  • Examples of the metal nano ink include a dispersion of coated silver ultrafine particles described in JP 2010-265543 A, a dispersion of coated copper fine particles described in JP 2012-72418 A, and JP 2012-162757 A.
  • Dispersion of coated metal fine particles described in Japanese Laid-Open Patent Publication dispersion of coated silver fine particles described in Japanese Patent Laid-Open No. 2014-31542, dispersion of coated silver fine particles described in Japanese Patent Laid-Open No. 2014-40630, International Publication Examples thereof include, but are not limited to, a dispersion of coated silver ultrafine particles described in No. 2011/119630.
  • Encapsulation of metal nano ink (low-temperature sintered ink) is appropriately performed according to the polarity of the ink solvent using known methods such as interfacial reaction method, in situ polymerization method, submerged curing coating method, phase separation method and submerged drying method. It can be used while adjusting.
  • the capsule wall 101 is not particularly limited as long as the encapsulated metal nano ink 102 can be released outside the capsule at a desired timing.
  • the capsule is destroyed.
  • the destruction is preferably, for example, a physical process in which the capsule is destroyed by applying pressure to the capsule and deforming it.
  • a process of dissolving the capsules by applying heat to such an extent that the metal nano ink to be contained is not changed is also preferable.
  • the capsule wall is composed of a polymer containing a photochromic material, spiropyrans, azobenzenes, diarylethenes, or stilbenes
  • the molecules isomerize and change the molecular structure when irradiated with light.
  • the volume and electronic structure of the capsule wall change, and the degree of interaction with the encapsulated ink and the mechanical strength can be changed.
  • the pH around the capsule the ionization state of the amino group, carboxy group, and hydroxy group is changed, and the physical properties of the capsule wall are controlled through changes in the compatibility of the polymer and changes in volume accompanied by electrostatic repulsion. Is also possible.
  • a capsule may be directly constituted by the above stimuli-responsive material, for example, it may be dispersed in the capsule as an additive.
  • the capsule wall 101 is preferably composed of a hydrophilic compound derivative. This is because, in the case of a dispersion described later, an aqueous dispersion can be obtained and handling becomes easy.
  • the hydrophilic compound derivative preferably has a water contact angle of 90 ° or less. This is because the hydrophilicity is sufficient when the contact angle with respect to water is 90 ° or less.
  • the contact angle with respect to water is a contact angle measured by JIS R 3257: 1999 “Test method for wettability of substrate glass surface”.
  • hydrophilic compound derivative for example, an alginate gel obtained by crosslinking a water-soluble alginate with polyvalent metal ions (for example, Ca 2+ , Fe 2+ , Fe 3+ , Al 3+, etc.) or acrylamide can be crosslinked.
  • polyvalent metal ions for example, Ca 2+ , Fe 2+ , Fe 3+ , Al 3+, etc.
  • Polyacrylamide gel Polyacrylamide gel, agarose gel made by cooling after dissolving agarose, poly (meth) acrylic acid made by polymerizing (meth) acrylic acid, a mixture of acrylate and UV reactive polymerization initiator (UV is irradiated during encapsulation ), Spiropyrans, azobenzenes, diarylethenes, photoresponsive polymers in which stilbenes are modified in the polymer skeleton, pH responsive polymers having many amino groups, carboxy groups or hydroxy groups, such as polyvinylpyrrolidine and polyethyleneimine, From the layer of ionic liquid and fluororesin Examples thereof include an electric field responsive polymer in which ions easily move when a voltage such as gel is applied. These can be used alone or in combination of two or more.
  • the encapsulated metal nanoink of the present invention may be dispersed in a dispersion medium to form a dispersion of encapsulated metal nanoink.
  • a dispersion By using a dispersion, the storage stability of the encapsulated metal nanoink can be further enhanced.
  • the dispersion medium is not particularly limited, but water or a hydrophilic solvent is preferable in consideration of dispersion stability when the capsule is composed of a hydrophilic compound derivative.
  • hydrophilic solvent examples include water-soluble alcohols, ethers derived from water-soluble alcohols, esters derived from water-soluble alcohols, and the like.
  • the water-soluble alcohol is preferably an aliphatic alcohol having 1 to 3 hydroxy groups in one molecule. Specifically, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-pentanol, Hexanol, cyclohexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, glycidol, methylcyclohexanol, 2-methyl-1-butanol, 3-methyl-2-butanol, 4-methyl-2-pen Tanol, isopropyl alcohol, 2-ethylbutanol, 2-ethylhexanol, 2-octanol, terpineol, dihydroterpineol, 2-methoxyethanol, 2-ethoxyethanol, 2-n-butoxyethanol, carbitol, ethyl carbitol, n- Spotted Carbitol, diacetone alcohol, ethylene glyco
  • ether derived from the water-soluble alcohol examples include diethyl ether, diisobutyl ether, dibutyl ether, methyl-t-butyl ether, methyl cyclohexyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and tetrahydrofuran. , Tetrahydropyran, 1,4-dioxane and the like.
  • ester derived from the water-soluble alcohol examples include methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, and ⁇ -butyrolactone.
  • Example 1 (1) Preparation of Encapsulated Metal Nano Ink Metal nano ink (hereinafter sometimes referred to as “room temperature sintered ink”) was prepared by the method described in Example 1 of JP2012-162767. 1.0 g of sodium alginate was weighed and dissolved in milli-Q water, and the total amount was made up to 100 mL to prepare a 1.0% (w / v) sodium alginate aqueous solution. 1.0% (w / v) aqueous sodium alginate solution and room temperature sintered ink were added dropwise from separate syringe devices into 20% (w / v) aqueous calcium chloride solution.
  • the room temperature sintered ink wrapped in the sodium alginate aqueous solution is dropped into the calcium chloride aqueous solution, and the sodium alginate aqueous solution quickly gels and burns at room temperature.
  • the ink was included (FIG. 2).
  • an encapsulated metal nanoink in which a room temperature sintered ink was encapsulated in a capsule made of calcium alginate was taken out from the calcium chloride aqueous solution and air-dried at room temperature for 24 hours to prepare an encapsulated metal nanoink.
  • the encapsulated metal nanoink was placed on another glass substrate and left at room temperature for 24 hours. After storage, the storage stability of the encapsulated metal nano-ink is evaluated by checking with the naked eye whether the encapsulated metal nano-ink is different from before storage, specifically whether the solvent has evaporated. did. The storage stability evaluation results are shown in the corresponding column of Table 1. “G” (Good) means that the solvent has not evaporated (storage stability), and “NG” (No-Good) means that the solvent has evaporated (no storage stability). (Hereinafter, the same applies to Examples and Comparative Examples). After evaluating the storage stability, the capsule was crushed by applying a load of about 1 kgf to the capsule.
  • the coating film was dried at room temperature for 24 hours to form a conductive film on the glass substrate.
  • the volume resistivity of the conductive film was measured by the method described above. The measured volume resistivity is shown in the corresponding column of Table 1.
  • the SEM image of the electrically conductive film was image
  • Example 2 (1) Preparation of Encapsulated Metal Nano Ink
  • Metal nano ink was prepared by the method described in Example 4 of JP 2012-162767 A (hereinafter sometimes referred to as “low temperature sintered ink”). This low-temperature sintered ink can form a conductive film by heating and baking the coating film.
  • An encapsulated metal nano-ink was prepared in the same manner as in Example 1 except that the prepared low-temperature sintered ink was used instead of the room temperature sintered ink used in Example 1.
  • this coating film was heat-treated at 100 ° C. for 2 hours to form a conductive film on the glass substrate.
  • the volume resistivity of this conductive film (volume resistivity of the fired coating film) was measured using the method described above. The measured volume resistivity is shown in the corresponding column of Table 1. The volume resistivity of the conductive film was measured using the method described above. The measured volume resistivity is shown in the corresponding column of Table 1.
  • the encapsulated metal nano-ink was placed on another glass substrate and left at room temperature for 24 hours. After being allowed to stand, the storage stability of the encapsulated metal nano ink was evaluated by the above-described evaluation method and evaluation criteria. The storage stability evaluation results are shown in the corresponding column of Table 1. After evaluating the storage stability, the capsule was crushed by applying a load of about 1 kgf to the capsule. The low-temperature sintered ink contained in the capsule spread on the glass substrate to form a coating film. After the coating film was dried at room temperature for 24 hours, a heat treatment was performed at 100 ° C. for 2 hours to form a conductive film on the glass substrate. The volume resistivity of this conductive film was measured using the method described above. The obtained volume resistivity is shown in the corresponding column of Table 1.
  • Example 1 The room temperature sintered ink prepared in Example 1 was applied onto a glass substrate by spin coating and allowed to stand at room temperature for 24 hours. After standing, the storage stability of the low-temperature sintered nano ink was evaluated by the above-described evaluation method and evaluation criteria. The storage stability evaluation results are shown in the corresponding column of Table 1. After evaluating the storage stability, the volume resistivity of the conductive film formed on the glass substrate was measured using the method described above. The obtained volume resistivity is shown in the corresponding column of Table 1. Moreover, the SEM image of the electrically conductive film was image
  • Example 2 The low-temperature sintered ink prepared in Example 2 was applied on a glass substrate by spin coating and allowed to stand at room temperature for 24 hours. After standing, the storage stability of the low-temperature sintered nano ink was evaluated by the above-described evaluation method and evaluation criteria. The storage stability evaluation results are shown in the corresponding column of Table 1. After evaluating the storage stability, the volume resistivity of the conductive film formed on the glass substrate was measured using the method described above. The obtained volume resistivity is shown in the corresponding column of Table 1. Moreover, the SEM image of the electrically conductive film was image
  • Table 1 summarizes the results of the examples and comparative examples.
  • Example 1 is an example using room temperature sintered ink. After crushing a capsule on a glass substrate, it was dried at room temperature for 24 hours, whereby good conductivity (3.082 ⁇ 10 ⁇ 5 ⁇ ) was formed on the substrate. A conductive film showing cm) could be formed. FIG. 5 suggests that large-sized particles produced by fusing silver nanoparticles are fused together to form a dense metal film. From these results, it is suggested that the encapsulated room temperature sintered ink is not altered even after encapsulation. In addition, after placing the encapsulated metal nano ink on a glass substrate and leaving it to stand at room temperature for 24 hours, the capsule is crushed and dried at room temperature for 24 hours, so that good conductivity (3.116 ⁇ 10 ⁇ is applied on the substrate).
  • FIG. 6 suggests that, as in FIG. 5, large-sized particles generated by fusing silver nanoparticles are fused together to form an ultra-dense metal film. From these results, the encapsulated metal nano ink of the present invention can form a conductive film having excellent conductivity by arbitrarily setting the timing to start forming the conductive film after being applied on the substrate, It is suggested to have on-demand characteristics.
  • Example 2 is an example using a low-temperature sintered ink. After crushing a capsule on a glass substrate, it was dried at room temperature for 24 hours, and further heat-treated at 100 ° C. for 2 hours, which was excellent on the substrate. A conductive film exhibiting conductivity (1.590 ⁇ 10 ⁇ 5 ⁇ ⁇ cm) could be formed. This result suggests that the encapsulated low-temperature sintered ink has not deteriorated even after encapsulation.
  • This low-temperature sintered ink is capable of forming a conductive film having excellent conductivity on a substrate by performing a heat treatment at 100 to 120 ° C. for 1 to 4 hours.
  • FIG. 7 suggests that the fusion of the silver nanoparticles does not proceed sufficiently, the formation of large-sized particles is not sufficient, and a dense conductive film is not formed.
  • the capsule was crushed after being left at room temperature for 24 hours, dried at room temperature for 24 hours, and further subjected to a heat treatment at 100 ° C. for 2 hours to form a substrate on the substrate.
  • a conductive film exhibiting excellent conductivity (1.584 ⁇ 10 ⁇ 5 ⁇ ⁇ cm) could be formed. From this result, the encapsulated metal nano-ink of the present invention can form a conductive film having excellent conductivity by arbitrarily setting the timing at which the conductive film starts to be formed after being applied on the substrate. It is suggested that there is demand.
  • Comparative Example 1 is an example using room temperature sintered ink that is not encapsulated in a capsule, and after applying by spin coating on a glass substrate, it is allowed to stand at room temperature for 24 hours and dried, thereby providing good conductivity on the substrate.
  • FIG. 8 suggests that, as in FIG. 5, large-sized particles produced by fusing silver nanoparticles are fused together to form an ultra-dense metal film.
  • the volatilization of the ink solvent proceeded and a conductive film began to be formed. Since this room temperature sintered ink starts forming the conductive film immediately after being applied on the substrate, the timing for forming the conductive film cannot be arbitrarily set, suggesting that it does not have on-demand properties. .
  • Comparative Example 2 is an example using low-temperature sintered ink that is not encapsulated in a capsule, and after applying by spin coating on a glass substrate, it is left to dry at room temperature for 24 hours to form a conductive film on the substrate. did. From FIG. 9, as in FIG. 7, the fusion of the silver nanoparticles does not proceed sufficiently, the formation of large-sized particles is not sufficient, and it is suggested that a dense conductive film is not formed. . Immediately after the low-temperature sintered ink was applied on the substrate, the volatilization of the ink solvent proceeded and a conductive film began to be formed. Since the formation of the conductive film starts immediately after the low-temperature sintered ink is applied on the substrate, the timing for forming the conductive film cannot be arbitrarily set, suggesting that it does not have on-demand properties. .
  • the encapsulated low-temperature sintered ink used in the present invention it is possible to increase the storage stability of the low-temperature sintered ink and to form a conductive metal thin film at an arbitrary timing.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Powder Metallurgy (AREA)
  • Conductive Materials (AREA)
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Abstract

L'invention concerne une nano-encre métallique encapsulée comprenant une pluralité de nanoparticules métalliques revêtues présentant un agent de protection à l'intérieur de la capsule, la capsule pouvant être détruite par stimulation externe de manière à former un film mince conducteur.
PCT/JP2015/074566 2014-09-10 2015-08-31 Composite comprenant une composition de fines particules métalliques revêtues WO2016039189A1 (fr)

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JP5925928B1 (ja) * 2015-02-26 2016-05-25 日本航空電子工業株式会社 電気接続構造および電気接続部材
CN110233170B (zh) 2019-06-21 2021-10-12 京东方科技集团股份有限公司 显示基板及其制作方法、显示装置
CN110729071B (zh) 2019-12-19 2020-06-09 北京梦之墨科技有限公司 液态金属导电浆料及电子器件
JP6952101B2 (ja) * 2019-12-27 2021-10-20 花王株式会社 金属微粒子含有インク

Citations (8)

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JP2004224835A (ja) * 2003-01-20 2004-08-12 Toppan Forms Co Ltd 導電性高分子マイクロカプセルインクおよびそれを用いたシート
JP2006111761A (ja) * 2004-10-15 2006-04-27 Mitsubishi Pencil Co Ltd 筆記具用インキ組成物及びこのインキ組成物を用いた筆記具
JP2006152121A (ja) * 2004-11-29 2006-06-15 Olympus Corp 画像形成用インク及び画像形成方法
JP2006299348A (ja) * 2005-04-20 2006-11-02 Seiko Epson Corp マイクロカプセル化金属粒子及びその製造方法、水性分散液、並びに、インクジェット用インク
JP2008300046A (ja) * 2007-05-29 2008-12-11 Mitsuboshi Belting Ltd 被覆組成物及び導電膜
JP2012162767A (ja) * 2011-02-04 2012-08-30 Yamagata Univ 被覆金属微粒子とその製造方法
WO2014021270A1 (fr) * 2012-08-02 2014-02-06 株式会社ダイセル Procédé permettant de fabriquer de l'encre qui contient des nanoparticules d'argent et encre contenant des nanoparticules d'argent
WO2014024630A1 (fr) * 2012-08-07 2014-02-13 田中貴金属工業株式会社 Encre à base de particules d'argent, corps fritté à base de particules d'argent et procédé de production de ladite encre

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004224835A (ja) * 2003-01-20 2004-08-12 Toppan Forms Co Ltd 導電性高分子マイクロカプセルインクおよびそれを用いたシート
JP2006111761A (ja) * 2004-10-15 2006-04-27 Mitsubishi Pencil Co Ltd 筆記具用インキ組成物及びこのインキ組成物を用いた筆記具
JP2006152121A (ja) * 2004-11-29 2006-06-15 Olympus Corp 画像形成用インク及び画像形成方法
JP2006299348A (ja) * 2005-04-20 2006-11-02 Seiko Epson Corp マイクロカプセル化金属粒子及びその製造方法、水性分散液、並びに、インクジェット用インク
JP2008300046A (ja) * 2007-05-29 2008-12-11 Mitsuboshi Belting Ltd 被覆組成物及び導電膜
JP2012162767A (ja) * 2011-02-04 2012-08-30 Yamagata Univ 被覆金属微粒子とその製造方法
WO2014021270A1 (fr) * 2012-08-02 2014-02-06 株式会社ダイセル Procédé permettant de fabriquer de l'encre qui contient des nanoparticules d'argent et encre contenant des nanoparticules d'argent
WO2014024630A1 (fr) * 2012-08-07 2014-02-13 田中貴金属工業株式会社 Encre à base de particules d'argent, corps fritté à base de particules d'argent et procédé de production de ladite encre

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