WO2016052033A1 - 銀粒子塗料組成物 - Google Patents

銀粒子塗料組成物 Download PDF

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WO2016052033A1
WO2016052033A1 PCT/JP2015/074488 JP2015074488W WO2016052033A1 WO 2016052033 A1 WO2016052033 A1 WO 2016052033A1 JP 2015074488 W JP2015074488 W JP 2015074488W WO 2016052033 A1 WO2016052033 A1 WO 2016052033A1
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Prior art keywords
silver
aliphatic hydrocarbon
coating composition
monoamine
amine
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PCT/JP2015/074488
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English (en)
French (fr)
Japanese (ja)
Inventor
宏禎 小妻
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株式会社ダイセル
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Application filed by 株式会社ダイセル filed Critical 株式会社ダイセル
Priority to CN201580052434.9A priority Critical patent/CN106715609A/zh
Priority to JP2016551656A priority patent/JP6564385B2/ja
Priority to KR1020177010981A priority patent/KR20170063784A/ko
Publication of WO2016052033A1 publication Critical patent/WO2016052033A1/ja

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    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver

Definitions

  • the present invention relates to a silver particle-containing coating composition.
  • the silver particle coating composition of the present invention is suitable for intaglio offset printing applications such as gravure offset printing. Moreover, this invention is applied also to the metal particle containing coating composition containing metals other than silver.
  • Silver nanoparticles can be sintered even at low temperatures. Utilizing this property, in the manufacture of various electronic devices, a silver coating composition containing silver nanoparticles is used to form electrodes and conductive circuit patterns on a substrate. Silver nanoparticles are usually dispersed in an organic solvent. Silver nanoparticles have an average primary particle size of about several nanometers to several tens of nanometers, and the surface thereof is usually coated with an organic stabilizer (protective agent). When the substrate is a plastic film or sheet, it is necessary to sinter the silver nanoparticles at a low temperature (for example, 200 ° C. or less) lower than the heat resistance temperature of the plastic substrate.
  • a low temperature for example, 200 ° C. or less
  • Japanese Patent Application Laid-Open No. 2010-265543 discloses a silver compound that decomposes by heating to produce metallic silver, a medium / short chain alkylamine having a boiling point of 100 ° C. to 250 ° C., and a medium / short chain alkyl diamine having a boiling point of 100 ° C. to 250 ° C.
  • a method for producing coated silver ultrafine particles comprising a first step of preparing a complex compound containing a silver compound, the alkylamine and the alkyldiamine, and a second step of thermally decomposing the complex compound is disclosed. (Claim 3, paragraphs [0061] and [0062]).
  • Japanese Patent Application Laid-Open No. 2012-162767 discloses a mixture of an amine mixture 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.
  • a method for producing coated metal fine particles which includes a first step of producing a complex compound containing, and a second step of thermally decomposing the complex compound to produce metal fine particles (Claim 1). It is also disclosed that the coated silver fine particles can be dispersed in an organic solvent such as an alcohol solvent such as butanol, a nonpolar solvent such as octane, or a mixed solvent thereof (paragraph [0079]).
  • Japanese Patent Application Laid-Open No. 2013-142172 and International Publication No. WO2013 / 105530 disclose a method for producing silver nanoparticles comprising an aliphatic hydrocarbon group and one amino group, and the carbon of the aliphatic hydrocarbon group.
  • Method for producing nanoparticles have been disclosed (claim 1).
  • a silver coating composition called a so-called silver ink can be prepared by dispersing the obtained silver nanoparticles in a suspended state in an appropriate organic solvent (dispersion medium).
  • organic solvent dispersing the obtained silver nanoparticles in a suspended state in an appropriate organic solvent (dispersion medium).
  • organic solvent such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, etc .; methanol, ethanol, propanol Alcohol solvents such as n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol and the like have been disclosed (paragraph [0085]).
  • Japanese Patent Application Laid-Open No. 2013-142173 and International Publication No. WO2013 / 105531 disclose a method for producing silver nanoparticles, which is composed of an aliphatic hydrocarbon group and one amino group, and the carbon of the aliphatic hydrocarbon group.
  • An aliphatic hydrocarbon monoamine (A) having a total number of 6 or more, and an aliphatic hydrocarbon monoamine (A) having an aliphatic hydrocarbon group and one amino group, wherein the total number of carbons of the aliphatic hydrocarbon group is 5 or less ( B) is prepared in a specific ratio, and a silver compound and the amine mixture are mixed to form a complex compound containing the silver compound and the amine, and the complex compound is heated.
  • a method for producing silver nanoparticles comprises thermally decomposing and forming silver nanoparticles (claim 1). Further, similarly to the above-mentioned JP2013-142172A, a silver coating composition called a so-called silver ink is obtained by dispersing the obtained silver nanoparticles in a suitable organic solvent (dispersion medium) in a suspended state. And similar organic solvents are disclosed (paragraph [0076]).
  • WO2014 / 021270 includes an aliphatic hydrocarbon monoamine (A) composed of an aliphatic hydrocarbon group and one amino group, the total number of carbons of the aliphatic hydrocarbon group being 6 or more, An aliphatic hydrocarbon monoamine (B) comprising an aliphatic hydrocarbon group and one amino group, and the total number of carbons of the aliphatic hydrocarbon group being 5 or less, and an aliphatic hydrocarbon group and two amino groups, And an amine containing at least one of the aliphatic hydrocarbon diamines (C) having a total number of carbon atoms of the aliphatic hydrocarbon group of 8 or less and a silver compound, the silver compound and the amine A silver-containing complex compound, and the complex compound is heated and thermally decomposed to form silver nanoparticles, and the silver nanoparticles are dispersed in a dispersion solvent containing an alicyclic hydrocarbon.
  • A aliphatic hydrocarbon monoamine
  • B comprising an aliphatic hydro
  • WO2014 / 024721 discloses a branched aliphatic hydrocarbon monoamine comprising a branched aliphatic hydrocarbon group and one amino group, wherein the branched aliphatic hydrocarbon group has 4 or more carbon atoms ( An aliphatic amine containing at least D) and a silver compound are mixed to form a complex compound containing the silver compound and the amine, and the complex compound is heated and thermally decomposed to form silver nanoparticles. A method for producing silver nanoparticles is disclosed (claim 1).
  • Japanese Patent Application Laid-Open No. 2010-55807 discloses a conductive paste used in an intaglio offset printing method using a silicone blanket made of silicone rubber, which includes a binder resin, a conductive powder, a high swelling solvent, and a low and high swelling solvent.
  • An electrically conductive paste containing a mixed solvent is disclosed (claim 1).
  • Silver powder is mentioned as the conductive powder (paragraph [0033]). It is disclosed that the 50% cumulative diameter D 50 of the particle size distribution is preferably 0.05 ⁇ m or more and 10 ⁇ m or less, particularly preferably 0.1 ⁇ m or more and 2 ⁇ m or less, and the conductive powder is a flaky conductive powder and a spherical conductive powder.
  • Japanese Patent Application Laid-Open No. 2010-55807 does not disclose silver nanoparticles whose surface is coated with a protective agent containing an aliphatic hydrocarbon amine. Moreover, there is no disclosure about the conductive performance.
  • Japanese Patent Application Laid-Open No. 2010-90211 discloses a conductive ink composition containing conductive particles and an organic vehicle containing a resin composition and a solvent (Claim 1), and an epoxy resin is used as the resin composition.
  • the use is disclosed (Claim 3), and the conductive particles are disclosed to be Ag particles (Claim 10).
  • the conductive ink composition is used for forming electrodes by intaglio offset printing (paragraph [0001]).
  • the conductive particles are disclosed to contain spherical conductive particles having an average particle diameter of 0.05 ⁇ m to 3 ⁇ m and flaky conductive particles having an average flake diameter of 0.1 ⁇ m or more and less than 3 ⁇ m (paragraph [0014]). ).
  • Japanese Patent Application Laid-Open No. 2010-90211 does not disclose silver nanoparticles whose surface is coated with a protective agent containing an aliphatic hydrocarbon amine.
  • the firing conditions in the examples are not described (paragraph [0027] and the like), and there is no disclosure of conductive performance by low-temperature firing.
  • JP 2011-37999 A discloses a conductive powder, a resin that is solid at 25 ° C., a monomer component selected from an oxetane monomer, an epoxy monomer, and a vinyl ether monomer, a polymerization initiator, and a specific organic compound.
  • a conductive ink containing a solvent and having a viscosity at 25 ° C. of 3 to 30 Pa ⁇ s is disclosed (Claim 1).
  • As the conductive powder a spherical silver powder having an average particle diameter of 1 ⁇ m or less and an average particle diameter of 1 ⁇ m are disclosed. Combining with spherical silver powder of 3 ⁇ m or less is disclosed (paragraph [0017]).
  • JP 2011-37999 A does not disclose silver nanoparticles whose surface is coated with a protective agent containing an aliphatic hydrocarbon amine.
  • JP 2012-38615 A contains silver particles, a resin that is solid at 25 ° C., and an organic cyclic ether compound (bifunctional oxetane compound), and has a viscosity at 25 ° C. of 3 to 30 Pa ⁇ s.
  • a conductive silver paste is disclosed (Claims 1, 2 and 3), and as silver particles, a median diameter (D50) of 0.2 to about 100 parts by mass of silver particles having a median diameter (D50) of 1.0 to 10.0 ⁇ m is disclosed. It is disclosed that 50 to 200 parts by mass of 0.9 ⁇ m silver particles are used in combination (claim 6, paragraph [0012]).
  • Silver nanoparticles have an average primary particle diameter of about several nanometers to several tens of nanometers, and are more likely to aggregate than micron ( ⁇ m) size particles. Therefore, the reduction reaction of the silver compound (thermal decomposition reaction in the above Patent Documents 1 to 9) is performed so that the surface of the obtained silver nanoparticles is coated with an organic stabilizer (protective agent such as aliphatic amine or aliphatic carboxylic acid). ) Is carried out in the presence of an organic stabilizer.
  • an organic stabilizer protecting agent such as aliphatic amine or aliphatic carboxylic acid
  • the silver nanoparticles are a silver coating composition (silver ink, silver paste) containing the particles in an organic solvent.
  • the organic stabilizer In order to develop conductivity, it is necessary to remove the organic stabilizer covering the silver nanoparticles and sinter the silver particles at the time of firing after application on the substrate. If the firing temperature is low, the organic stabilizer is difficult to remove. If the degree of sintering of the silver particles is not sufficient, a low resistance value cannot be obtained. That is, the organic stabilizer present on the surface of the silver nanoparticles contributes to the stabilization of the silver nanoparticles, but prevents the silver nanoparticles from being sintered (particularly, sintering at low temperature firing).
  • an aliphatic amine compound and / or an aliphatic carboxylic acid compound having a relatively long chain for example, having 8 or more carbon atoms
  • the distance between the individual silver nanoparticles is easily secured. Nanoparticles are easy to stabilize.
  • long-chain aliphatic amine compounds and / or aliphatic carboxylic acid compounds are difficult to remove if the firing temperature is low.
  • Patent Documents 10 to 13 do not disclose silver nanoparticles whose surface is coated with a protective agent containing an aliphatic hydrocarbon amine, and that sufficient electrical conductivity is obtained by low-temperature firing. There is no disclosure.
  • an object of the present invention is to provide a silver particle coating composition that exhibits excellent conductivity (low resistance value) by firing at a low temperature for a short time.
  • Patent Documents 11 to 13 disclose using a curable component.
  • An initiator is required to cure the curable component.
  • an object of the present invention is to provide a silver particle paint composition that exhibits excellent conductivity (low resistance value) by firing at a low temperature for a short time and has excellent adhesion between the silver coating film (silver fired film) and the substrate. To provide things.
  • the silver particle coating composition when used for intaglio offset printing, it is necessary to improve the transferability of the silver coating composition from the blanket to the substrate to be printed.
  • intaglio offset printing first, the silver coating composition should be filled in the concave portions of the intaglio, and the silver coating composition filled in the concave portions should be transferred to a blanket (usually made of silicone rubber) and then printed from the blanket. Transfer the silver paint composition to the substrate.
  • the blanket sucks and swells the solvent of the silver coating composition to some extent, and thereby the adhesion between the silver coating composition and the blanket surface is lowered, the transferability from the blanket to the substrate is improved.
  • the fine line drawability (straight line drawability) is improved.
  • an object of the present invention is to exhibit excellent conductivity (low resistance value) by firing at a low temperature for a short time, to have excellent adhesion between the silver coating film (silver fired film) and the substrate, and to draw fine lines.
  • Another object of the present invention is to provide a silver coating composition suitable for intaglio offset printing, which has excellent properties.
  • the inventors of the present invention use silver nanoparticles prepared by a so-called pyrolysis method and having a surface coated with a protective agent containing an aliphatic hydrocarbon amine, and a vinyl chloride-vinyl acetate copolymer resin. It came to complete.
  • the present invention includes the following inventions.
  • Silver nanoparticles (N) whose surface is coated with a protective agent containing an aliphatic hydrocarbon amine, A vinyl chloride-vinyl acetate copolymer resin; A silver particle coating composition comprising a dispersion solvent.
  • the aliphatic hydrocarbon amine includes an aliphatic hydrocarbon monoamine (A) composed of an aliphatic hydrocarbon group and one amino group, and the total number of carbon atoms of the aliphatic hydrocarbon group is 6 or more. Furthermore, an aliphatic hydrocarbon monoamine (B) comprising an aliphatic hydrocarbon group and one amino group, and the total number of carbons of the aliphatic hydrocarbon group being 5 or less, and an aliphatic hydrocarbon group and two amino groups
  • the silver particle coating composition according to (1) above which comprises at least one of aliphatic hydrocarbon diamines (C) having the total number of carbon atoms of the aliphatic hydrocarbon group of 8 or less.
  • the aliphatic hydrocarbon monoamine (A) has a linear alkyl monoamine having a linear alkyl group having 6 to 12 carbon atoms and a branched alkyl group having 6 to 16 carbon atoms.
  • the silver particle coating composition according to the above (2) which is at least one selected from the group consisting of branched alkyl monoamines.
  • the aliphatic hydrocarbon diamine (C) is an alkylene diamine in which one of the two amino groups is a primary amino group and the other is a tertiary amino group (2
  • the aliphatic hydrocarbon amine includes the aliphatic hydrocarbon monoamine (A), the aliphatic hydrocarbon monoamine (B), and the aliphatic hydrocarbon diamine (C).
  • the silver particle coating composition according to any one of the above.
  • the silver nanoparticles (N) Mixing the aliphatic hydrocarbon amine as a protective agent and a silver compound to produce a complex compound containing the silver compound and the amine, It can be formed by heating and thermally decomposing the complex compound.
  • the silver compound is preferably silver oxalate.
  • Silver oxalate molecules contain two silver atoms.
  • the aliphatic hydrocarbon amine is preferably used in a total amount of 2 to 100 moles per mole of silver oxalate.
  • the silver particle coating composition according to any one of (1) to (8) used for intaglio offset printing includes gravure offset printing.
  • a method of manufacturing an electronic device comprising: Calcination can be performed at a temperature of 200 ° C. or lower, such as 150 ° C. or lower, preferably 120 ° C. or lower, for 2 hours or shorter, such as 1 hour or shorter, preferably 30 minutes or shorter, more preferably 15 minutes or shorter. More specifically, it can be performed under conditions of about 90 ° C. to 120 ° C., about 10 minutes to 15 minutes, for example, 120 ° C. for 15 minutes.
  • Metal nanoparticles whose surface is coated with a protective agent containing an aliphatic hydrocarbon amine, A vinyl chloride-vinyl acetate copolymer resin; A metal particle coating composition comprising a dispersion solvent.
  • the substrate may be selected from a plastic substrate, a ceramic substrate, a glass substrate, and a metal substrate.
  • the silver particle coating composition comprises silver nanoparticles (N) whose surface is coated with a protective agent containing an aliphatic hydrocarbon amine, a vinyl chloride-vinyl acetate copolymer resin, and a dispersion solvent. It is out.
  • Silver nanoparticles (N) whose surfaces are coated with a protective agent containing an aliphatic hydrocarbon amine are prepared by a so-called thermal decomposition method of a silver complex compound.
  • a protective agent containing an aliphatic hydrocarbon amine is prepared by a so-called thermal decomposition method of a silver complex compound.
  • the aliphatic hydrocarbon amine compound that functions as a complexing agent and / or a protective agent an aliphatic hydrocarbon monoamine (A) having 6 or more carbon atoms and an aliphatic hydrocarbon monoamine (B) having 5 or less carbon atoms.
  • aliphatic hydrocarbon diamines (C) having a total carbon number of 8 or less, the surface of the formed silver nanoparticles is coated with these aliphatic amine compounds.
  • the aliphatic hydrocarbon monoamine (B) and the aliphatic hydrocarbon diamine (C) have a short carbon chain length, they are calcined at a low temperature of 200 ° C. or lower, for example 150 ° C. or lower, preferably 120 ° C. or lower. In addition, it is easily removed from the surface of the silver particles in a short time of 2 hours or less, for example 1 hour or less, preferably 30 minutes or less. Further, due to the presence of the monoamine (B) and / or the diamine (C), the amount of the aliphatic hydrocarbon monoamine (A) deposited on the silver particle surface can be small. Accordingly, even in the case of firing at the low temperature, these aliphatic amine compounds are easily removed from the surface of the silver particles in the short time, and the sintering of the silver particles proceeds sufficiently.
  • the vinyl chloride-vinyl acetate copolymer resin functions as a binder resin.
  • the silver particle coating composition is applied (or printed) on the substrate to be printed and baked, and the adhesion between the silver coating film (baked silver film) and the substrate. Excellent. Further, the viscosity of the coating composition can be adjusted with a vinyl chloride-vinyl acetate copolymer resin.
  • the silver particle coating composition can have a viscosity suitable for intaglio offset printing applications such as gravure offset printing. Therefore, in the intaglio offset printing, the transferability from the blanket to the substrate is improved, and the fine line drawability (straight line drawability) is improved.
  • a silver particle coating composition (silver particle-containing ink or silver particle-containing paste) that exhibits excellent conductivity (low resistance value) by firing at a low temperature for a short time. Is done.
  • excellent conductivity is exhibited by baking at a low temperature for a short time, excellent adhesion between the silver coating film (silver baking film) and the substrate, and fine line drawing.
  • a silver coating composition suitable for intaglio offset printing having excellent properties is provided.
  • the silver coating composition further contains silver microparticles (M)
  • the silver nanoparticles (N) are in the gaps between the silver microparticles (M) in the coating layer of the coating composition on the substrate. It has entered. If it does so, the contact efficiency between silver nanoparticle (N) and silver microparticle (M) will become good, and electroconductivity will improve by baking.
  • the silver particle coating composition of the present invention when the silver nanoparticles (N) (and the silver microparticles (M) when used) are dispersed in a dispersion solvent containing a glycol ester solvent, With such a dispersion solvent, when the coating composition is used for intaglio offset printing, the transferability of silver ink from the blanket to the substrate is improved.
  • intaglio offset printing first, the silver coating composition is filled into the recesses of the intaglio, and the silver coating composition filled in the recesses is transferred to a blanket (usually made of silicone rubber), and then silver is transferred from the blanket to the substrate. Transfer the coating composition. At this time, it is considered that the blanket sucks the solvent of the silver coating composition to some extent and swells, thereby reducing the adhesion between the silver coating composition and the blanket surface and improving the transferability from the blanket to the substrate.
  • the present invention is also applicable to a metal particle coating composition containing a metal other than silver.
  • a conductive film and conductive wiring can be formed on various plastic substrates having low heat resistance such as PET and polypropylene, preferably by intaglio offset printing.
  • the silver particle coating composition of the present invention is suitable for device applications of various recent electronic devices.
  • 2 is a photograph (x100) obtained by observing a silver ink fine line produced in Example 1 with a CCD.
  • 2 is a photograph (x100) obtained by observing a silver ink fine line produced in Comparative Example 1 with a CCD.
  • the silver particle coating composition of the present invention comprises silver nanoparticles (N) whose surface is coated with a protective agent containing an aliphatic hydrocarbon amine, silver microparticles (M) when used, and vinyl chloride-vinyl acetate. It contains a copolymer resin and a dispersion solvent.
  • the silver particle coating composition includes both so-called silver ink and silver paste.
  • Silver nanoparticles (N) whose surface is coated with an aliphatic hydrocarbon amine protecting agent
  • Silver nanoparticles (N) are mixed with an aliphatic hydrocarbon amine and a silver compound to produce a complex compound containing the silver compound and the amine, It can be produced by heating and complexing the complex compound.
  • the method for producing silver nanoparticles (N) mainly includes a complex compound generation step and a complex compound thermal decomposition step. The obtained silver nanoparticles (N) are subjected to a dispersion process for preparing a coating composition.
  • the term “nanoparticle” means that the size of the primary particles (average primary particle diameter) determined by observation with a scanning electron microscope (SEM) is less than 1000 nm.
  • the particle size is intended to exclude the protective agent (stabilizer) present (coated) on the surface (that is, the size of silver itself).
  • the silver nanoparticles have an average primary particle size of, for example, 0.5 nm to 100 nm, preferably 0.5 nm to 80 nm, more preferably 1 nm to 70 nm, and still more preferably 1 nm to 60 nm.
  • the silver compound a silver compound that is easily decomposed by heating to form metallic silver is used.
  • silver compounds include silver formate, silver acetate, silver oxalate, silver malonate, silver benzoate, and silver phthalate; silver fluoride, silver chloride, silver bromide, silver iodide, etc.
  • Silver sulfate; silver sulfate, silver nitrate, silver carbonate, and the like can be used, but silver oxalate is preferably used from the viewpoint that metal silver is easily generated by decomposition and impurities other than silver are hardly generated.
  • Silver oxalate is advantageous in that it has a high silver content and does not require a reducing agent, so that metallic silver can be obtained as it is by thermal decomposition, and impurities derived from the reducing agent do not easily remain.
  • a metal compound that is easily decomposed by heating to produce a target metal is used instead of the silver compound.
  • a metal salt corresponding to the above silver compound for example, a metal carboxylate; a metal halide; a metal salt compound such as a metal sulfate, a metal nitrate, or a metal carbonate is used. be able to.
  • metal oxalate is preferably used from the viewpoint of easily generating metal by decomposition and hardly generating impurities other than metal.
  • other metals include Al, Au, Pt, Pd, Cu, Co, Cr, In, and Ni.
  • the above silver compound and a metal compound other than the above silver may be used in combination.
  • other metals include Al, Au, Pt, Pd, Cu, Co, Cr, In, and Ni.
  • the silver composite is composed of silver and one or more other metals, and examples thereof include Au—Ag, Ag—Cu, Au—Ag—Cu, and Au—Ag—Pd. Based on the total metal, silver accounts for at least 20% by weight, usually at least 50% by weight, for example at least 80% by weight.
  • the aliphatic hydrocarbon amine and the silver compound may be mixed without solvent, but in the presence of an alcohol solvent having 3 or more carbon atoms, the silver compound and the silver compound are mixed. It is preferable to form a complex compound containing an amine.
  • an alcohol having 3 to 10 carbon atoms preferably an alcohol having 4 to 6 carbon atoms can be used.
  • n-propanol (boiling point bp: 97 ° C.), isopropanol (bp: 82 ° C.), n-butanol (bp: 117 ° C.), isobutanol (bp: 107.89 ° C.), sec-butanol (bp: 99.
  • n-butanol, isobutanol, sec-butanol the convenience of post-treatment after the formation of the silver nanoparticles can be increased in consideration of the ability to increase the temperature of the thermal decomposition step of the complex compound performed later.
  • Butanols and hexanols selected from tert-butanol are preferred. In particular, n-butanol and n-hexanol are preferable.
  • the alcohol solvent is, for example, 120 parts by weight or more, preferably 130 parts by weight or more, more preferably 150 parts by weight with respect to 100 parts by weight of the silver compound for sufficient stirring operation of the silver compound-alcohol slurry. It is good to use above.
  • the upper limit of the amount of the alcohol solvent is not particularly limited, and is, for example, 1000 parts by weight or less, preferably 800 parts by weight or less, more preferably 500 parts by weight or less with respect to 100 parts by weight of the silver compound. .
  • the mixing of the aliphatic hydrocarbon amine and the silver compound in the presence of an alcohol solvent having 3 or more carbon atoms may take several forms.
  • a solid silver compound and an alcohol solvent are mixed to obtain a silver compound-alcohol slurry [slurry forming step], and then an aliphatic hydrocarbon amine is added to the obtained silver compound-alcohol slurry. It may be added.
  • the slurry represents a mixture in which a solid silver compound is dispersed in an alcohol solvent.
  • a slurry may be obtained by charging a solid silver compound into a reaction vessel and adding an alcohol solvent thereto.
  • an aliphatic hydrocarbon amine and an alcohol solvent may be charged into a reaction vessel, and a silver compound-alcohol slurry may be added thereto.
  • the aliphatic hydrocarbon amine that functions as a complexing agent and / or a protective agent includes, for example, an aliphatic hydrocarbon monoamine (A) in which the total number of carbon atoms of the hydrocarbon group is 6 or more, and an aliphatic group.
  • An aliphatic hydrocarbon monoamine (B) consisting of a hydrocarbon group and one amino group, wherein the aliphatic hydrocarbon group has a total carbon number of 5 or less, and consisting of an aliphatic hydrocarbon group and two amino groups; You may use at least one of the aliphatic hydrocarbon diamine (C) whose carbon total number of this aliphatic hydrocarbon group is 8 or less.
  • Each of these components is usually used as an amine mixed solution.
  • the mixing of the amine with the silver compound (or the alcohol slurry thereof) is not necessarily performed using the mixed amines.
  • the amines may be sequentially added to the silver compound (or alcohol slurry thereof).
  • an “aliphatic hydrocarbon monoamine” is a compound composed of 1 to 3 monovalent aliphatic hydrocarbon groups and one amino group.
  • a “hydrocarbon group” is a group consisting only of carbon and hydrogen.
  • the aliphatic hydrocarbon monoamine (A) and the aliphatic hydrocarbon monoamine (B) are, as necessary, a hetero atom (an atom other than carbon and hydrogen) such as an oxygen atom or a nitrogen atom. ). This nitrogen atom does not constitute an amino group.
  • aliphatic hydrocarbon diamine means a divalent aliphatic hydrocarbon group (alkylene group), two amino groups intervening the aliphatic hydrocarbon group, and, in some cases, hydrogen of the amino group. It is a compound comprising an aliphatic hydrocarbon group (alkyl group) substituted with atoms.
  • the aliphatic hydrocarbon diamine (C) may have a substituent containing a hetero atom (atom other than carbon and hydrogen) such as an oxygen atom or a nitrogen atom in the hydrocarbon group as necessary. Good. This nitrogen atom does not constitute an amino group.
  • the aliphatic hydrocarbon monoamine (A) having a total carbon number of 6 or more has a high function as a protective agent (stabilizer) on the surface of the silver particles to be generated by the hydrocarbon chain.
  • the aliphatic hydrocarbon monoamine (A) includes primary amines, secondary amines, and tertiary amines.
  • primary amines include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine
  • saturated aliphatic hydrocarbon monoamines having a linear aliphatic hydrocarbon group having 6 to 18 carbon atoms such as amines (that is, alkyl monoamines).
  • saturated aliphatic hydrocarbon monoamine in addition to the above linear aliphatic monoamine, a branched chain having 6 to 16 carbon atoms, preferably 6 to 8 carbon atoms such as isohexylamine, 2-ethylhexylamine, tert-octylamine, etc. And branched aliphatic hydrocarbon monoamines having a linear aliphatic hydrocarbon group. Also included is cyclohexylamine. Furthermore, unsaturated aliphatic hydrocarbon monoamines (namely, alkenyl monoamines) such as oleylamine can be mentioned.
  • Secondary amines are linear, such as 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-methyl-N-propylamine, N-ethyl-N-propyl Examples thereof include dialkyl monoamines such as amine and N-propyl-N-butylamine. Examples of the tertiary amine include tributylamine and trihexylamine.
  • examples of branched ones include secondary amines such as N, N-diisohexylamine and N, N-di (2-ethylhexyl) amine.
  • secondary amines such as N, N-diisohexylamine and N, N-di (2-ethylhexyl) amine.
  • tertiary amines such as triisohexylamine and tri (2-ethylhexyl) amine can be mentioned.
  • N, N-di (2-ethylhexyl) amine the 2-ethylhexyl group has 8 carbon atoms, but the total number of carbons contained in the amine compound is 16.
  • tri (2-ethylhexyl) amine the total number of carbons contained in the amine compound is 24.
  • a saturated aliphatic hydrocarbon monoamine having 6 or more carbon atoms is preferable.
  • the upper limit of the number of carbon atoms is not particularly defined, but saturated aliphatic monoamines having up to 18 carbon atoms are usually preferred in consideration of availability, ease of removal during firing, and the like.
  • alkyl monoamines having 6 to 12 carbon atoms such as hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, and dodecylamine are preferably used.
  • alkyl monoamines having 6 to 12 carbon atoms such as hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, and dodecylamine are preferably used.
  • linear aliphatic hydrocarbon monoamines only one type may be used, or two or more types may be used in combination.
  • the steric factor of the branched aliphatic hydrocarbon group leads to the surface of the silver particle.
  • a larger area of the silver particle surface can be coated with a smaller amount of adhesion. Therefore, moderate stabilization of the silver nanoparticles can be obtained with a smaller amount of adhesion on the surface of the silver particles. Since the amount of protective agent (organic stabilizer) to be removed at the time of firing is small, the organic stabilizer can be efficiently removed even when firing at a low temperature of 200 ° C. or less, and the silver particles are sufficiently sintered. To do.
  • branched alkyl monoamine compounds having 5 to 6 carbon atoms in the main chain such as isohexylamine and 2-ethylhexylamine are preferable.
  • the main chain has 5 to 6 carbon atoms, appropriate stabilization of the silver nanoparticles can be easily obtained.
  • it is effective to branch at the second carbon atom from the N atom side, such as 2-ethylhexylamine.
  • said branched aliphatic monoamine only 1 type may be used and it may be used in combination of 2 or more type.
  • the linear aliphatic hydrocarbon monoamine and the branched aliphatic hydrocarbon monoamine may be used in combination in order to obtain respective advantages.
  • the aliphatic hydrocarbon monoamine (B) having a total carbon number of 5 or less has a shorter carbon chain length than the aliphatic monoamine (A) having a total carbon number of 6 or more, it itself has a low function as a protective agent (stabilizer).
  • the polarity is higher and the coordination ability of the silver compound to silver is higher, which is considered to be effective in promoting complex formation.
  • the carbon chain length is short, it can be removed from the surface of the silver particles in a short time of 30 minutes or less or 20 minutes or less even in low-temperature firing of 120 ° C. or less, or about 100 ° C. or less. Effective for low-temperature firing of silver nanoparticles.
  • Examples of the aliphatic hydrocarbon monoamine (B) include ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopentylamine, tert-pentylamine and the like.
  • Examples thereof include saturated aliphatic hydrocarbon monoamines having 2 to 5 carbon atoms (that is, alkyl monoamines).
  • dialkyl monoamines such as N, N-dimethylamine and N, N-diethylamine are also included.
  • n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopentylamine, tert-pentylamine and the like are preferable, and the above butylamines are particularly preferable.
  • the aliphatic hydrocarbon monoamines (B) only one type may be used, or two or more types may be used in combination.
  • Aliphatic hydrocarbon diamine (C) having a total carbon number of 8 or less has high coordination ability to silver of silver compounds and is effective in promoting complex formation.
  • the aliphatic hydrocarbon diamine generally has a higher polarity than the aliphatic hydrocarbon monoamine, and the coordination ability of silver compounds to silver is increased.
  • the aliphatic hydrocarbon diamine (C) has an effect of promoting thermal decomposition at a lower temperature and in a shorter time in the thermal decomposition step of the complex compound, and can produce silver nanoparticles more efficiently. .
  • the protective film of the silver particle containing the said aliphatic diamine (C) has high polarity, the dispersion stability of the silver particle in the dispersion medium containing a highly polar solvent improves. Furthermore, since the aliphatic diamine (C) has a short carbon chain length, the surface of the silver particles can be obtained in a short time of 30 minutes or less or 20 minutes or less even when firing at a low temperature of 120 ° C. or less or about 100 ° C. or less. Therefore, it is effective for low-temperature and short-time firing of the obtained silver nanoparticles.
  • the aliphatic hydrocarbon diamine (C) is not particularly limited, but includes ethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, 1 , 3-propanediamine, 2,2-dimethyl-1,3-propanediamine, N, N-dimethyl-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-butanediamine, N, N-diethyl-1,4-butanediamine, N, N′-diethyl-1,4-butanediamine 1,5-pentanediamine, 1,5-d
  • alkylene diamines having a total carbon number of 8 or less, in which at least one of the two amino groups is a primary amino group or a secondary amino group, and the ability of the silver compound to coordinate to silver is high, Effective in promoting complex formation.
  • one of the two amino groups is a primary amino group
  • An alkylenediamine having a total carbon number of 8 or less, wherein —NH 2 ) and the other one is a tertiary amino group (—NR 1 R 2 ) is preferred.
  • a preferred alkylenediamine is represented by the following structural formula.
  • R represents a divalent alkylene group
  • R 1 and R 2 may be the same or different and each represents an alkyl group, provided that the total number of carbon atoms of R, R 1 and R 2 is 8
  • the alkylene group usually does not contain a hetero atom (an atom other than carbon and hydrogen) such as an oxygen atom or a nitrogen atom, but may optionally have a substituent containing the hetero atom.
  • the alkyl group usually does not contain a heteroatom such as an oxygen atom or a nitrogen atom, but may optionally have a substituent containing the heteroatom.
  • one of the two amino groups is a primary amino group
  • the ability of the silver compound to coordinate to silver is increased, which is advantageous for complex formation
  • the other is a tertiary amino group. Since the tertiary amino group has poor coordination ability to silver atoms, the complex formed is prevented from having a complex network structure.
  • a high temperature may be required for the thermal decomposition process of the complex.
  • a diamine having a total carbon number of 6 or less is preferable, and a diamine having a total carbon number of 5 or less is more preferable from the viewpoint that it can be removed from the surface of the silver particles in a short time even in low-temperature firing.
  • the aliphatic hydrocarbon diamine (C) only one type may be used, or two or more types may be used in combination.
  • the aliphatic hydrocarbon monoamine (A) having 6 or more carbon atoms the aliphatic hydrocarbon monoamine (B) having 5 or less carbon atoms, and the aliphatic hydrocarbon diamine (C) having 8 or less carbon atoms.
  • the use ratio with either one or both is not particularly limited, but based on the total amines [(A) + (B) + (C)], for example, Aliphatic monoamine (A): 5 mol% to 65 mol% Total amount of the aliphatic monoamine (B) and the aliphatic diamine (C): 35 mol% to 95 mol% It is good to do.
  • the function of protecting and stabilizing the surface of the silver particles produced can be easily obtained by the carbon chain of the component (A).
  • the protective stabilization function may be weakly expressed.
  • the protective stabilization function is sufficient, but the component (A) is difficult to be removed by low-temperature firing.
  • aliphatic monoamine (A) and both the aliphatic monoamine (B) and the aliphatic diamine (C) are used, their use ratio is not particularly limited, but the total amines Based on [(A) + (B) + (C)], for example, Aliphatic monoamine (A): 5 mol% to 65 mol% Aliphatic monoamine (B): 5 mol% to 70 mol% Aliphatic diamine (C): 5 mol% to 50 mol% It is good to do.
  • the branched aliphatic monoamine is used as the component (A)
  • the aliphatic monoamine (A): 5 mol% to 65 mol% is satisfied.
  • Branched aliphatic monoamine 10 mol% to 50 mol% It is good to do.
  • the lower limit of the content of the component (A) is preferably 10 mol% or more, more preferably 20 mol% or more.
  • the content of the aliphatic monoamine (B) By setting the content of the aliphatic monoamine (B) to 5 mol% to 70 mol%, a complex formation promoting effect can be easily obtained, and it can contribute itself to low temperature and short time baking. In this case, the effect of assisting the removal of the aliphatic diamine (C) from the surface of the silver particles is easily obtained. If the content of the component (B) is less than 5 mol%, the effect of promoting complex formation may be weak, or the component (C) may be difficult to remove from the surface of the silver particles during firing. On the other hand, when the content of the component (B) exceeds 70 mol%, a complex formation promoting effect can be obtained, but the content of the aliphatic monoamine (A) is relatively decreased, and silver particles are generated.
  • the aliphatic diamine (C) By setting the content of the aliphatic diamine (C) to 5 mol% to 50 mol%, a complex formation promoting effect and a thermal decomposition promoting effect of the complex can be easily obtained, and the aliphatic diamine (C) is contained. Since the protective film of silver particles has a high polarity, the dispersion stability of silver particles in a dispersion medium containing a highly polar solvent is improved. When the content of the component (C) is less than 5 mol%, the complex formation promoting effect and the thermal decomposition promoting effect of the complex may be weak.
  • the content of the component (C) exceeds 50 mol%, the complex formation promoting effect and the thermal decomposition promoting effect of the complex are obtained, but the content of the aliphatic monoamine (A) is relatively reduced. Therefore, it is difficult to achieve protection and stabilization of the surface of the silver particles to be produced.
  • About the minimum of content of the said (C) component 5 mol% or more is preferable and 10 mol% or more is more preferable.
  • About the upper limit of content of the said (C) component 45 mol% or less is preferable and 40 mol% or less is more preferable.
  • aliphatic monoamine (A) and the aliphatic monoamine (B) are used (without using the aliphatic diamine (C)), their use ratio is not particularly limited. Considering the action, based on the total amines [(A) + (B)], for example, Aliphatic monoamine (A): 5 mol% to 65 mol% Aliphatic monoamine (B): 35 mol% to 95 mol% It is good to do. When the branched aliphatic monoamine is used as the component (A), the aliphatic monoamine (A): 5 mol% to 65 mol% is satisfied. Branched aliphatic monoamine: 10 mol% to 50 mol% It is good to do.
  • the use ratio thereof is not particularly limited. Considering the action, based on the total amines [(A) + (C)], for example, Aliphatic monoamine (A): 5 mol% to 65 mol% Aliphatic diamine (C): 35 mol% to 95 mol% It is good to do.
  • Aliphatic monoamine (A) 5 mol% to 65 mol%
  • Aliphatic diamine (C) 35 mol% to 95 mol% It is good to do.
  • the branched aliphatic monoamine is used as the component (A)
  • the aliphatic monoamine (A): 5 mol% to 65 mol% is satisfied.
  • Branched aliphatic monoamine 10 mol% to 50 mol% It is good to do.
  • the above-mentioned use ratios of the aliphatic monoamine (A), the aliphatic monoamine (B) and / or the aliphatic diamine (C) are all examples, and various changes are possible.
  • the total number of carbons is 6 depending on the use ratio thereof.
  • the adhesion amount of the above aliphatic monoamine (A) on the silver particle surface is small. Therefore, even in the case of firing at a low temperature for a short time, these aliphatic amine compounds are easily removed from the surface of the silver particles, and the sintering of the silver particles (N) proceeds sufficiently.
  • the total amount of the aliphatic hydrocarbon amine is not particularly limited, but is 1 mol of silver atoms of the silver compound as a raw material.
  • the amount is preferably about 1 to 50 mol.
  • the total amount [(A), (B) and / or (C)] of the amine component is less than 1 mole relative to 1 mole of the silver atom, it is converted into a complex compound in the complex compound formation step.
  • a silver compound that is not left will remain, and in the subsequent pyrolysis step, the uniformity of the silver particles may be impaired, resulting in enlargement of the particles, or the silver compound may remain without being thermally decomposed.
  • the total amount of the amine component is preferably about 2 mol or more, for example, and the total amount of the amine component is about 2 to 50 mol.
  • the lower limit of the total amount of the amine component is preferably 2 mol or more with respect to 1 mol of silver atoms of the silver compound. More preferably, the silver oxalate molecule contains two silver atoms.
  • an aliphatic carboxylic acid (D) may be further used as a stabilizer.
  • the aliphatic carboxylic acid (D) is preferably used together with the amines, and can be used by being included in the amine mixed solution.
  • aliphatic carboxylic acid (D) a saturated or unsaturated aliphatic carboxylic acid is used.
  • aliphatic carboxylic acid a saturated or unsaturated aliphatic carboxylic acid is used.
  • saturated aliphatic monocarboxylic acids having 4 or more carbon atoms such as icosanoic acid and eicosenoic acid
  • unsaturated aliphatic monocarboxylic acids having 8 or more carbon atoms such as oleic acid
  • saturated or unsaturated aliphatic monocarboxylic acids having 8 to 18 carbon atoms are preferable.
  • the number of carbon atoms By setting the number of carbon atoms to 8 or more, when the carboxylic acid group is adsorbed on the surface of the silver particle, a space between the silver particle and other silver particles can be secured, so that the effect of preventing aggregation of the silver particles is improved.
  • saturated or unsaturated aliphatic monocarboxylic acid compounds having up to 18 carbon atoms are usually preferred.
  • octanoic acid, oleic acid and the like are preferably used.
  • the aliphatic carboxylic acids (D) only one type may be used, or two or more types may be used in combination.
  • the aliphatic carboxylic acid (D) When the aliphatic carboxylic acid (D) is used, it may be used in an amount of, for example, about 0.05 to 10 mol, preferably 0.1 to 5 mol, relative to 1 mol of silver atoms in the starting silver compound. More preferably 0.5 to 2 mol is used.
  • the amount of the component (D) When the amount of the component (D) is less than 0.05 mol with respect to 1 mol of the silver atom, the effect of improving the stability in the dispersed state by the addition of the component (D) is weak.
  • the amount of the component (D) reaches 10 mol, the effect of improving the stability in a dispersed state is saturated, and the component (D) is hardly removed by low-temperature firing.
  • the aliphatic carboxylic acid (D) may not be used.
  • a mixed liquid containing each aliphatic hydrocarbon amine component to be used for example, any of the aliphatic monoamine (A), the aliphatic monoamine (B), and the aliphatic diamine (C)
  • An amine mixture containing either or both is prepared [a step of preparing an amine mixture].
  • the amine mixed solution can be prepared by stirring each amine (A), (B) and / or (C) component, and, if used, the carboxylic acid (D) component at a predetermined ratio at room temperature. .
  • a metal compound (or alcohol slurry) containing the target metal is used instead of the silver compound (or alcohol slurry thereof).
  • a silver compound (or alcohol slurry thereof) or a metal compound (or alcohol slurry thereof) is mixed with a predetermined amount of an amine mixture.
  • Mixing may be performed at room temperature.
  • “Normal temperature” intends 5 to 40 ° C. depending on the ambient temperature. For example, 5 to 35 ° C (JIS Z 8703), 10 to 35 ° C, and 20 to 30 ° C are intended. It may be a normal room temperature (for example, a range of 15 to 30 ° C.).
  • the mixing is carried out with stirring or the coordination reaction of amines to the silver compound (or metal compound) is exothermic, so that the temperature is within the above range, for example, about 5 to 15 ° C. You may carry out, cooling suitably and stirring. If mixing of the silver compound and the amine mixture is performed in the presence of an alcohol having 3 or more carbon atoms, stirring and cooling can be performed satisfactorily. The excess of alcohol and amines serves as the reaction medium.
  • a liquid aliphatic amine component is first charged in a reaction vessel, and a powdery silver compound (silver oxalate) is charged therein.
  • the liquid aliphatic amine component is a flammable substance, and there is a danger in putting the powdered silver compound therein. That is, there is a risk of ignition due to static electricity due to the introduction of the silver compound of the powder. Moreover, there is a risk that the complex formation reaction proceeds locally due to the introduction of the powdered silver compound, and the exothermic reaction may explode. Such a danger can be avoided by mixing the silver compound and the amine mixture in the presence of the alcohol. Therefore, it is safe in scaled-up industrial production.
  • the complex compound to be formed generally exhibits a color corresponding to its constituent components
  • the end point of the complex compound formation reaction can be detected by detecting the end of the color change of the reaction mixture by appropriate spectroscopy or the like.
  • the complex compound formed by silver oxalate is generally colorless (observed as white when visually observed), but even in such a case, the complex compound is formed on the basis of a change in form such as a change in viscosity of the reaction mixture.
  • the generation state can be detected.
  • the complex reaction time is about 30 minutes to 3 hours. In this way, a silver-amine complex (or metal-amine complex) is obtained in a medium mainly composed of alcohol and amines.
  • the obtained complex compound is heated and pyrolyzed to form silver nanoparticles (N) [complex compound pyrolysis step].
  • a metal compound containing a metal other than silver is used, target metal nanoparticles are formed.
  • Silver nanoparticles (metal nanoparticles) are formed without using a reducing agent. However, if necessary, an appropriate reducing agent may be used as long as the effects of the present invention are not impaired.
  • amines control the manner in which atomic metals generated by the decomposition of metal compounds aggregate to form fine particles, and on the surface of the formed metal fine particles.
  • a film By forming a film, it plays the role of preventing reaggregation between the fine particles. That is, by heating a complex compound of a metal compound and an amine, the metal compound is thermally decomposed while maintaining the coordinate bond of the amine to the metal atom to produce an atomic metal, and then the amine is coordinated. It is considered that the metal atoms are aggregated to form metal nanoparticles covered with an amine protective film.
  • the thermal decomposition is preferably performed while stirring the complex compound in a reaction medium mainly composed of alcohol (when used) and amines.
  • the thermal decomposition is preferably performed within a temperature range in which the coated silver nanoparticles (or coated metal nanoparticles) are generated. From the viewpoint of preventing amine from being removed from the silver particle surface (or metal particle surface), the above temperature range is used. It is preferable to carry out at as low a temperature as possible.
  • a complex compound of silver oxalate it can be set to, for example, about 80 ° C. to 120 ° C., preferably about 95 ° C. to 115 ° C., more specifically about 100 ° C. to 110 ° C.
  • the thermal decomposition of the complex compound is preferably performed in an inert gas atmosphere such as argon, but the thermal decomposition can also be performed in the air.
  • stable coated silver nanoparticles (N) (or coated metal nanoparticles) can be obtained [post-treatment step of silver nanoparticles]. If it dries after washing
  • Use water or organic solvent for decantation and cleaning operations examples include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, and tetradecane; alicyclic hydrocarbon solvents such as cyclohexane; toluene, xylene, mesitylene, and the like
  • Aromatic hydrocarbon solvents such as: alcohol solvents such as methanol, ethanol, propanol, butanol, etc .; acetonitrile; and mixed solvents thereof may be used.
  • a glycol solvent may be used as the organic solvent for the decantation / cleaning operation.
  • the glycol solvent include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether (butyl carbitol: BC), ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene.
  • glycol monoethers such as glycol monomethyl ether.
  • the glycol solvent only one kind may be used, or two or more kinds may be used in combination.
  • silver nanoparticles (N) are obtained.
  • an appropriate reducing agent may be used as necessary as long as the effects of the present invention are not impaired.
  • the protective agent includes, for example, the aliphatic monoamine (A), and further includes one or both of the aliphatic monoamine (B) and the aliphatic diamine (C). Contains the carboxylic acid (D). Their content in the protective agent is equivalent to their use in the amine mixture. The same applies to metal nanoparticles.
  • the term “microparticle” means that the average particle diameter is 1 ⁇ m or more and 10 ⁇ m or less. Unlike the silver nanoparticle (N), the silver microparticle (M) does not have an aliphatic hydrocarbon amine protecting agent on the surface thereof.
  • the silver microparticles may be spherical particles or flaky particles.
  • the flaky particles are intended to have an aspect ratio, that is, a ratio of diameter to microparticle thickness (diameter / thickness) of, for example, 2 or more.
  • the flaky particles have a larger contact area between the particles than the spherical particles, and therefore the conductivity tends to be improved.
  • the average particle diameter of the silver microparticles (M) is such that the 50% cumulative diameter D50 of the particle size distribution is, for example, 1 ⁇ m to 5 ⁇ m, preferably 1 ⁇ m to 3 ⁇ m.
  • the silver microparticles include TC-507A (shape: flake shape, D50: 2.78 ⁇ m), TC-505C (shape: flake shape, D50: 2.18 ⁇ m) manufactured by Tokuhoku Chemical Laboratory Co., Ltd.
  • TC-905C shape: flake, D50: 1.21 ⁇ m
  • AgS-050 shape: spherical, D50: 1.4 ⁇ m
  • C-34 shape: spherical, D50: 0.6 ⁇ m
  • AG-2- 1C shape: spherical, 0.9 ⁇ m, manufactured by DOWA Electronics
  • the particle diameter is calculated by a laser diffraction method.
  • the mixing ratio of the silver nanoparticles (N) and the silver microparticles (M) is not particularly limited, but the silver nanoparticles (N) and Based on the total of silver microparticles (M), for example, Silver nanoparticles (N): 10 to 90% by weight Silver microparticles (M): 10 to 90% by weight It is good to do.
  • Silver microparticles (M) 10 to 90% by weight It is good to do.
  • the amount of the silver nanoparticles (N) is less than 10% by weight, there are few silver nanoparticles (N) entering the gaps between the silver microparticles (M), and the contact improving effect between the silver microparticles (M) is improved. It is difficult to obtain. Moreover, the effect of low-temperature firing of the silver nanoparticles (N) whose surface is coated with a protective agent containing an aliphatic hydrocarbon amine is also relatively reduced. For these reasons, it is difficult to obtain the effect of improving conductivity by low-temperature firing. On the other hand, when the amount of silver nanoparticles (N) exceeds 90% by weight, the storage stability of the silver coating composition may be lowered.
  • the silver nanoparticles (N) used in the present invention have a surface coated with a protective agent containing an aliphatic hydrocarbon amine and are excellent in low-temperature firing, but may be gradually sintered even during storage of the coating composition. is there. Sintering causes an increase in the viscosity of the coating composition. From such a viewpoint, it is preferable to use 10% by weight or more of silver microparticles (M) that are stable even at around room temperature.
  • Silver nanoparticles (N) 30-80% by weight Silver microparticles (M): 20 to 70% by weight And more preferably Silver nanoparticles (N): 50 to 75% by weight Silver microparticles (M): 25-50% by weight It is good to do.
  • the silver coating composition contains a vinyl chloride-vinyl acetate copolymer resin as a binder resin.
  • the silver fired film (conductive pattern) obtained by applying (or printing) on the substrate to be printed and firing is adhered to the substrate. And the flexibility of the fired silver film is improved.
  • the viscosity of the coating composition can be adjusted with a vinyl chloride-vinyl acetate copolymer resin.
  • the silver particle coating composition can have a viscosity suitable for intaglio offset printing applications such as gravure offset printing. Therefore, in the intaglio offset printing, the transferability from the blanket to the substrate is improved, and the fine line drawability (straight line drawability) is improved.
  • the vinyl chloride-vinyl acetate copolymer resin is not particularly limited, and various types can be used.
  • vinyl alcohol, hydroxy (meth) acrylate in vinyl chloride-vinyl acetate copolymer Those containing about 3 to 15% by weight of hydroxyl group-containing units such as esters are preferred.
  • the silver particles (N) and (M) can be more favorably dispersed, and the adhesion to the substrate is improved.
  • Solvent MIBK / toluene 1/1, B-type viscometer, 25 ° C.), K value 41];
  • Solvein series such as TA2, TA3, TAO (Manufactured by Nissin Chemical Industry).
  • the amount of the vinyl chloride-vinyl acetate copolymer resin added is, for example, about 0.1 wt% to 10 wt%, preferably about 2 wt% to 5 wt%, based on the silver coating composition. With the addition amount of vinyl chloride-vinyl acetate copolymer resin within this range, it is easy to obtain a silver particle coating composition having a viscosity suitable for intaglio offset printing applications such as gravure offset printing, and adhesion between the sintered silver film and the substrate. It is easy to improve the flexibility and the flexibility of the fired silver film.
  • binder resin in addition to the vinyl chloride-vinyl acetate copolymer resin, for example, polyvinyl butyral resin, polyester resin, acrylic resin, ethyl cellulose resin, and the effect of the vinyl chloride-vinyl acetate copolymer resin are used. You may use to such an extent that it does not reduce.
  • the polyvinyl butyral resin is not particularly limited, but preferably has a weight average molecular weight (Mw) of about 10,000 to 100,000.
  • Mw weight average molecular weight
  • SLECK B series manufactured by Sekisui Chemical Co., Ltd.
  • polyester-type resin for example, a polycaprolactone triol (Purcell 305 [PCL305] by Daicel Corporation) etc. are mentioned as a commercial item.
  • ETHOCEL registered trademark, Nisshin Kasei
  • Thermosetting resins such as phenolic resins, polyimide resins, melamine resins, melamine-polyester resins, and curable monomers such as oxetane monomers and epoxy monomers may be used. Care must be taken not to use harmful initiators (eg, antimony-based initiators) as initiators for curing. In the present invention, since the vinyl chloride-vinyl acetate copolymer resin is used, it is not necessary to use a curable component.
  • the dispersion solvent may be any solvent that can disperse the silver nanoparticles (N) and, if used, the silver microparticles (M) well and dissolve the vinyl chloride-vinyl acetate copolymer resin.
  • organic solvents for obtaining a silver coating composition include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, and tetradecane; alicyclic carbonization such as cyclohexane and methylcyclohexane Hydrogen solvent; aromatic hydrocarbon solvent such as toluene, xylene, mesitylene, etc .; methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n -Alcohol solvents such as decanol; glycol solvents; glycol ester solvents; terpene solvents such as terpineol and dihydroterpineol.
  • glycol solvent examples include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol mono, which are listed as organic solvents for the decantation and washing operation of the silver nanoparticles (N).
  • glycol monoethers such as butyl ether, diethylene glycol monobutyl ether (butyl carbitol: BC), propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.
  • glycol monoethers examples include diethylene glycol monohexyl ether (hexyl carbitol: HC) and diethylene glycol mono 2-ethylhexyl ether.
  • glycol solvent only one kind may be used, or two or more kinds may be used in combination.
  • the glycol solvent may be derived from the solvent used in the decantation / cleaning operation of the silver nanoparticles (N).
  • glycol ester solvent examples include glycol monoester solvents and glycol diester solvents.
  • glycol ester solvent examples include ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate (butyl carbaldehyde).
  • Glycol acetate monoesters such as tall acetate (BCA), propylene glycol monomethyl ether acetate (PMA; 1-methoxy-2-propyl acetate), dipropylene glycol monomethyl ether acetate); Ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, 1,4-butanediol diacetate (1,4-BDDA, boiling point 230 ° C.), 1,6-hexanediol diacetate (1 , 6-HDDA, boiling point 260 ° C.), glycol diesters such as 2-ethyl-1,6-hexanediol diacetate; Is exemplified.
  • the glycol ester solvent only one kind may be used, or two or more kinds may be used in combination.
  • the glycol solvent and the glycol ester solvent have a property of penetrating into a silicone blanket in intaglio offset printing.
  • the blanket-ink interface is dried, the adhesion between the ink and the blanket is reduced, and the transfer property of the ink from the blanket to the substrate is improved.
  • the dispersion solvents it is preferable to use a high boiling point solvent having a boiling point of 200 ° C. or more because these solvents are low in volatility and change in the concentration of silver ink hardly occurs, and also from the viewpoint of the working environment. Moreover, it is preferable to use at least the glycol diester (glycol diacetate) in the dispersion solvent.
  • the glycol diester (glycol diacetate) is preferably used because it easily dissolves the vinyl chloride-vinyl acetate copolymer resin.
  • the glycol monoether monoester generally has the highest permeability to silicone blankets.
  • the blanket is excessively swollen and the transfer property of the ink to the base material tends to be impaired. Therefore, in order to ensure appropriate penetrability of the dispersion solvent to the blanket, the glycol monoether, glycol diester, etc., which generally have lower penetrability to the silicone blanket than the glycol monoether monoester, may be used. preferable.
  • the total amount of the dispersion solvent is, for example, 20% by weight to 60% by weight, preferably 25% by weight to 50% by weight, more preferably 25% by weight or more, based on the silver coating composition. It is contained in the range of 40% by weight or less. From the viewpoint of intaglio offset printing application, when the amount of the dispersion solvent is less than 20% by weight, the amount of solvent is small, and transfer during printing may not be performed well. On the other hand, when the amount of the dispersion solvent exceeds 60% by weight, the amount of the solvent is large, fine line printing may not be performed satisfactorily, and low-temperature firing may not be performed satisfactorily.
  • the silver coating composition may further contain components other than those described above so as to meet the object of the present invention.
  • the viscosity of the silver coating composition is, for example, in a range of 0.1 Pa ⁇ s to 30 Pa ⁇ s in an environmental temperature condition (for example, 25 ° C.) at the time of printing in consideration of intaglio offset printing applications. Preferably, it is in the range of 5 Pa ⁇ s to 25 Pa ⁇ s. If the viscosity of the ink is less than 0.1 Pa ⁇ s, the fluidity of the ink is too high, and there is a risk of problems in accepting the ink from the intaglio to the blanket and transferring the ink from the blanket to the substrate to be printed. is there.
  • An ink (or paste) containing silver particles in a suspended state can be prepared by mixing and stirring the polymer resin and the dispersion solvent described above.
  • the said silver particle is based also on a use purpose, it is 10 weight% or more as a sum total of a silver nanoparticle (N) and a silver microparticle (M) in a silver particle containing ink, for example, 25 weight% or more, Preferably it is 30. It is good to make it contain in the ratio of the weight% or more.
  • the upper limit of the silver particle content is 80% by weight or less.
  • the mixing / dispersing of the coated silver nanoparticles (N) and silver microparticles (M), the vinyl chloride-vinyl acetate copolymer resin, and the dispersion solvent may be performed once or several times. May be.
  • the silver paint composition (silver ink) obtained by the present invention is excellent in stability.
  • the silver ink is stable, for example, at a silver concentration of 50% by weight without causing an increase in viscosity when stored at 5 ° C. in a refrigerator for a period of 1 month or more.
  • the prepared silver coating composition (silver ink) is applied onto a substrate by a known application method, for example, by an intaglio offset printing method, and then baked.
  • a patterned silver ink coating layer is obtained by intaglio offset printing, and the silver ink coating layer is fired to obtain a patterned silver conductive layer (silver fired film).
  • the silver ink is filled into the concave portion of the intaglio, and the silver ink filled in the concave portion is transferred to a blanket usually made of silicone rubber, and then the silver ink is transferred from the blanket to the substrate.
  • a glycol solvent and / or glycol ester solvent used as a dispersion solvent
  • the dispersion solvent infiltrates into the blanket and swells the blanket.
  • the concentration of the silver ink held on the blanket surface increases, that is, the drying proceeds. Thereby, the adhesion between the silver ink on the blanket surface and the blanket is lowered, and the transferability of the silver ink from the blanket to the substrate is improved.
  • the silver ink contains a vinyl chloride-vinyl acetate copolymer resin
  • the adhesion between the silver fired film obtained by applying (or printing) on the substrate to be printed and firing and the substrate is improved.
  • the flexibility of the fired film is improved.
  • Calcination can be performed at a temperature of 200 ° C. or lower, for example, room temperature (25 ° C.) or higher and 150 ° C. or lower, preferably room temperature (25 ° C.) or higher and 120 ° C. or lower. However, in order to complete the sintering of silver by firing in a short time, it is performed at a temperature of 60 ° C. or higher and 200 ° C. or lower, such as 80 ° C. or higher and 150 ° C. or lower, preferably 90 ° C. or higher. Good.
  • the firing time may be appropriately determined in consideration of the amount of silver ink applied, the firing temperature, etc., for example, within several hours (eg, 3 hours or 2 hours), preferably within 1 hour, more preferably within 30 minutes, More preferably, the time is 10 minutes to 30 minutes.
  • the silver nanoparticles are configured as described above, the sintering of the silver particles sufficiently proceeds even by such a firing process at a low temperature and in a short time. As a result, excellent conductivity (low resistance value) is exhibited.
  • a silver conductive layer having a low resistance value (for example, 15 ⁇ cm or less and in the range of 5 to 15 ⁇ cm) is formed.
  • the resistance value of bulk silver is 1.6 ⁇ cm.
  • the substrate can be a glass substrate, a heat resistant plastic substrate such as a polyimide film, or a polyester film such as a polyethylene terephthalate (PET) film or a polyethylene naphthalate (PEN) film.
  • a general-purpose plastic substrate having low heat resistance such as a polyolefin-based film such as polypropylene can also be suitably used.
  • baking in a short time reduces the load on these general-purpose plastic substrates having low heat resistance, and improves production efficiency.
  • the silver conductive material obtained by the present invention includes various electronic devices such as electromagnetic wave control materials, circuit boards, antennas, heat sinks, liquid crystal displays, organic EL displays, field emission displays (FEDs), IC cards, IC tags, solar It can be applied to batteries, LED elements, organic transistors, capacitors (capacitors), electronic paper, flexible batteries, flexible sensors, membrane switches, touch panels, EMI shields, and the like. In particular, it is effective for electronic materials that require surface smoothness, and for example, is effective as a gate electrode of a thin film transistor (TFT) in a liquid crystal display.
  • TFT thin film transistor
  • the thickness of the silver conductive layer may be appropriately determined according to the intended use. Without being particularly limited, for example, it may be selected from the range of 5 nm to 10 ⁇ m, preferably 100 nm to 5 ⁇ m, more preferably 300 nm to 2 ⁇ m.
  • the ink mainly containing silver nanoparticles has been described.
  • the present invention is also applied to ink containing metal nanoparticles containing a metal other than silver.
  • the obtained silver fired film was measured using a four-terminal method (Loresta GP MCP-T610).
  • the measuring range limit of this device is 10 7 ⁇ cm.
  • n-Butylamine (MW: 73.14): Reagent 2-ethylhexylamine (MW: 129.25) manufactured by Tokyo Chemical Industry Co., Ltd. Reagent n-octylamine (MW: 129.25) manufactured by Wako Pure Chemical Industries, Ltd .: manufactured by Tokyo Chemical Industry Co., Ltd. Reagent methanol: Wako Pure Chemical Co., Ltd. reagent special grade 1-butanol: Wako Pure Chemical Industries, Ltd.
  • Example 1 (Preparation of silver nanoparticles) A 500 mL flask was charged with 40.0 g (0.1317 mol) of silver oxalate, and 60 g of n-butanol was added thereto to prepare an n-butanol slurry of silver oxalate. To this slurry, an amine mixture of 115.58 g (1.5802 mol) of n-butylamine, 51.06 g (0.3950 mol) of 2-ethylhexylamine, and 17.02 g (0.1317 mol) of n-octylamine was added at 30 ° C. Was dripped. After the dropwise addition, the mixture was stirred at 30 ° C.
  • the wet silver nanoparticles were observed with a scanning electron microscope (JSM-6700F manufactured by JEOL Ltd.) by a conventional method, and the average particle size of the silver nanoparticles was determined. (Diameter) was about 50 nm.
  • the average particle size was determined as follows. The silver nanoparticles were subjected to SEM observation, the particle diameters of 10 silver particles arbitrarily selected in the SEM photograph were determined, and the average value thereof was taken as the average particle diameter.
  • Table 1 shows the composition of the silver ink.
  • the composition of each component is expressed in parts by weight with respect to 100 parts by weight as a whole.
  • the silver ink was applied on a soda glass plate to form a coating film. After forming the coating film, the coating film was quickly baked in an air-drying furnace at 120 ° C. for 30 minutes to form a 5 ⁇ m thick silver fired film. When the specific resistance value of the obtained silver fired film was measured by the four-terminal method, it showed a good conductivity of 10.1 ⁇ cm. As described above, the silver ink exhibited excellent conductivity by baking at a low temperature for a short time.

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DE112017004749T5 (de) 2016-09-21 2019-06-27 Yazaki Corporation Elektrisch leitfähige Paste und Leiterplatte damit
EP4059634A4 (en) * 2019-12-20 2023-08-23 Mitsubishi Materials Corporation SILVER PASTE AND METHOD FOR PRODUCTION THEREOF AND METHOD FOR PRODUCTION OF SOLDERED ARTICLE

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