WO2016031409A1 - Composition et procédé de formation d'un film conducteur - Google Patents

Composition et procédé de formation d'un film conducteur Download PDF

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Publication number
WO2016031409A1
WO2016031409A1 PCT/JP2015/070059 JP2015070059W WO2016031409A1 WO 2016031409 A1 WO2016031409 A1 WO 2016031409A1 JP 2015070059 W JP2015070059 W JP 2015070059W WO 2016031409 A1 WO2016031409 A1 WO 2016031409A1
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Prior art keywords
conductive film
cupric oxide
oxide nanoparticles
composition
forming
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PCT/JP2015/070059
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English (en)
Japanese (ja)
Inventor
佑一 早田
美里 佐々田
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富士フイルム株式会社
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Priority to JP2016545040A priority Critical patent/JP6263630B2/ja
Publication of WO2016031409A1 publication Critical patent/WO2016031409A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • 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
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic 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
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the present invention relates to a conductive film forming composition and a conductive film forming method.
  • this invention relates to the composition for electrically conductive film formation containing a cupric oxide nanoparticle and an alcohol compound.
  • a dispersion of metal particles or metal oxide particles is applied to the base material by a printing method, and heated and sintered, so that the electrical property such as wiring on the metal film or the circuit board is obtained.
  • a technique for forming an electrical conduction site is known. Since the above method is simpler, energy-saving, and resource-saving than conventional high-heat / vacuum processes (sputtering) and plating processes, it is highly anticipated in the development of next-generation electronics.
  • Patent Document 1 discloses copper, silver, or indium high-valent compound, linear, branched or cyclic alcohol having 1 to 18 carbon atoms and a group VIII metal catalyst, A composition for forming a conductive film of silver or indium is described. Moreover, the manufacturing method of the electrically conductive film of copper, silver, or indium characterized by forming a film
  • this invention makes it a subject to provide the composition for electrically conductive film formation which can form the electrically conductive film excellent in base-material adhesiveness and electroconductivity. Moreover, this invention also makes it a subject to provide the electrically conductive film formation method using the said composition for electrically conductive film formation.
  • the present inventors are a conductive film-forming composition containing cupric oxide nanoparticles and an alcohol compound, and the average of cupric oxide nanoparticles is 1 According to the conductive film-forming composition in which the secondary particle size, average aspect ratio and particle size distribution, and electrical conductivity of the conductive film-forming composition are controlled within a predetermined range, the substrate adhesion and conductivity are excellent. Knowing that a conductive film can be formed, the present invention has been completed.
  • the present invention provides the following (1) to (10).
  • a composition for forming a conductive film comprising cupric oxide nanoparticles and an alcohol compound,
  • the alcohol compound content is 20 to 1000 parts by mass with respect to 100 parts by mass of cupric oxide nanoparticles,
  • the average primary particle size of cupric oxide nanoparticles is 3 to 25 nm,
  • the average aspect ratio of the cupric oxide nanoparticles is more than 1.1 and not more than 5.0,
  • the ratio of particles having a primary particle diameter exceeding 30 nm among cupric oxide nanoparticles is less than 30%, and the electrical conductivity of the composition for forming a conductive film is 2 to 240 mS / m.
  • Composition Composition.
  • composition for electrically conductive film formation as described in (1) which is a nanoparticle by which the cupric oxide nanoparticle was granulated by the wet granulation method.
  • the total content of the fine particles of Group 8 to 10 heavy metal element and the salt of Group 8 to 10 heavy metal element is 0.01 to 10 parts by mass with respect to 100 parts by mass of cupric oxide nanoparticles.
  • a conductive film forming method comprising a step of heating a film precursor film at a temperature of 110 ° C. or higher and 150 ° C. or lower in an inert gas atmosphere to form a conductive film on a resin substrate.
  • the composition for electrically conductive film formation which can form the electrically conductive film excellent in base-material adhesiveness and electroconductivity can be provided. Moreover, this invention can also provide the electrically conductive film formation method using the said composition for electrically conductive film formation.
  • the conductive film formed using the composition for forming a conductive film of the present invention has excellent substrate adhesion and conductivity, and can meet the recent demands for downsizing and high functionality of electronic devices.
  • a characteristic point of the present invention is that the content of the alcohol compound is 20 to 1000 parts by mass with respect to 100 parts by mass of cupric oxide nanoparticles, and the average primary particle diameter of cupric oxide nanoparticles is 3
  • the electric conductivity of the composition for forming a conductive film is 2 to 240 mS / m.
  • the characteristic points of the present invention are not limited to these.
  • Patent Document 1 copper (I) oxide, copper oxide (II) or copper nitride (I) is desirable as the high valence compound of copper, and its shape Describes that particles are preferable in that a metal film having high density can be obtained, and that the average particle diameter is desirably 5 nm to 500 ⁇ m.
  • the content ratio between the high valence compound of copper and the alcohol, the particle size distribution of the particles, and the average aspect ratio there is no description regarding the electrical conductivity of the conductive film forming composition. From the results of Examples and Comparative Examples to be described later, those skilled in the art can understand that the technique described in Patent Document 1 does not necessarily form a conductive film excellent in substrate adhesion and conductivity. Will.
  • the content ratio between the cupric oxide nanoparticles and the alcohol compound is specified, and not only the average primary particle size of the cupric oxide nanoparticles but also the particle size distribution and the average aspect ratio are specified. Furthermore, the base-material adhesiveness and electroconductivity of the electrically conductive film obtained become excellent by making electric conductivity of the composition for electrically conductive film into the predetermined range.
  • composition for electrically conductive film formation of this invention contains a cupric oxide nanoparticle.
  • cupric oxide is reduced to metallic copper by a sintering treatment described later, and constitutes a metal conductor in the conductive film.
  • cupric oxide in the present invention is a compound that does not substantially contain copper that has not been oxidized and cuprous oxide, and specifically, a crystal by X-ray diffraction (XRD: X-ray Diffraction).
  • XRD X-ray Diffraction
  • peaks derived from cupric oxide strong diffraction peaks derived from (002) and (111) planes near 35.5 ° and 38 °, respectively
  • the phrase “substantially free of unoxidized copper and cuprous oxide” means that the content of metal copper and cuprous oxide is 1% by mass or less with respect to cupric oxide.
  • the average primary particle diameter of cupric oxide nanoparticles is 3 to 25 nm, preferably 5 to 20 nm, and more preferably 5 to 15 nm. Within this range, good dispersion stability can be obtained, and reduction from cupric oxide to metallic copper is easy, and even when sintered at a lower sintering temperature, the conductive film has high conductivity. Can be produced.
  • the average primary particle diameter of cupric oxide nanoparticles is the horizontal ferret diameter and vertical of 1000 particles randomly selected from a scanning electron microscope (hereinafter sometimes referred to as “SEM”) image.
  • SEM scanning electron microscope
  • the ferret diameter is measured, and the measured value of the smaller one is calculated as the primary particle diameter of the particles by arithmetic averaging.
  • either measurement value may be used.
  • the average aspect ratio of the cupric oxide nanoparticles is more than 1.1 and 5.0 or less, preferably 1.2 or more and 4.0 or less, more preferably 1.2 or more and 3.0 or less, It is more preferably 2.5 or more and 2.5 or less, and still more preferably 1.2 or more and 2.0 or less.
  • the average aspect ratio is obtained by measuring and averaging the aspect ratios of the 1000 particles. When the average aspect ratio is within this range, the base material adhesion and conductivity of the obtained conductive film are more excellent. This is probably because the cupric oxide nanoparticles have a more spherical shape, so that the filling rate is increased and a denser conductive film can be formed.
  • the average aspect ratio of cupric oxide nanoparticles is calculated by dividing the smaller measured value of the horizontal ferret diameter and the vertical ferret diameter of 1000 randomly selected particles by the smaller measured value. This is the average of the values obtained.
  • the proportion of particles having a primary particle diameter exceeding 30 nm is less than 30%, preferably less than 20%, and less than 15%. More preferably, it is less than 10%, more preferably less than 5%.
  • a synthesis method (granulation method) of cupric oxide nanoparticles there are a dry granulation method in which granulation is performed in a gas phase and a wet granulation method in which granulation is performed in a liquid phase.
  • a wet granulation method is suitable for producing particles having a smaller diameter.
  • a dispersion of copper hydroxide particles is produced by reacting a divalent copper salt such as copper nitrate with a base in a solvent. Then, a method of synthesizing cupric oxide by heating and dehydrating copper hydroxide to obtain a dispersion of cupric oxide nanoparticles is preferable.
  • the cupric oxide nanoparticles are blended in the state of a dispersion, so that if the amount of electrolytic mass brought in is large, the electrical conductivity of the composition for forming a conductive film falls within a predetermined range. This is because it becomes difficult to fit in the substrate, and the base material adhesion and conductivity of the obtained conductive film deteriorate.
  • the dispersion is centrifuged to recover cupric oxide nanoparticles, and water or a polyhydric alcohol having a boiling point of 150 to 300 ° C. is used.
  • a method of repeating the operation of redispersing in the dispersion medium once or more, preferably 2 times or more, more preferably 3 times or more can be mentioned.
  • Centrifugal force at the time of centrifugation is not particularly limited, preferably 5000 ⁇ g or more, preferably 10,000 ⁇ g or more, more preferably 20000 ⁇ g or more, in order to avoid excessive aggregation of cupric oxide nanoparticles, 30000xg or less is preferable.
  • the electrolyte may be removed by a method such as ultrafiltration or dialysis, but is not limited thereto.
  • the polyhydric alcohol having a boiling point of 150 to 300 ° C. may be an alcohol compound or a solvent that can be used as a solvent described later.
  • the composition for electrically conductive film formation of this invention contains an alcohol compound.
  • the alcohol compound functions as a reducing agent that reduces cupric oxide of the cupric oxide nanoparticles to metallic copper.
  • the alcohol compound include methanol, ethanol, propanol, 2-propanol, allyl alcohol, butanol, 2-butanol, pentanol, 2-pentanol, 3-pentanol, cyclopentanol, hexanol, 2-hexanol, 3-hexanol, cyclohexanol, heptanol, 2-heptanol, 3-heptanol, 4-heptanol, cycloheptanol, octanol, 2-octanol, 3-octanol, 4-octanol, cyclooctanol, nonanol, 2- Nonanol, 3,5,5-trimethyl-1-hexanol, 3-methyl-3-octanol, 3-ethyl-2,2-dimethyl-3-pentanol, 2,6-dimethyl-4-heptanol, decanol, 2 -
  • Glycerol propane-1,2,3-triol
  • butane-1,2,4-triol hexane-1,2,6-triol
  • 3-methylpentane-1,3,5-triol trimethylol Propane
  • 2- hydroxymethyl Trivalent alcohols such as -2-ethylpropane-1,3-diol
  • cyclooctane-1,3,5,7-tetraol pentaerythritol
  • 2,2-bis (hydroxymethyl) -1,3- And tetrahydric alcohols such as propanediol.
  • the alcohol compound is not particularly limited as long as it is a compound having one or more alcoholic hydroxy groups in the molecule, but a polyhydric alcohol having two or more alcoholic hydroxy groups in the molecule is preferred, and a divalent or trivalent alcohol is preferred. More preferred is trivalent alcohol.
  • the alcohol compound preferably has a boiling point of 180 ° C. or higher, more preferably 230 ° C. or higher, and further preferably 250 ° C. or higher.
  • the polyhydric alcohol When a polyhydric alcohol having a boiling point of 180 ° C. or higher is used, the polyhydric alcohol remains in the film even during the sintering process of the cupric oxide nanoparticles, and the cupric oxide can be sufficiently reduced to metallic copper.
  • the resulting conductive film has good conductivity, and when a polyhydric alcohol having a boiling point of 250 ° C. or higher is used, the substrate adhesion is further improved. Examples of the polyhydric alcohol having a boiling point of 180 ° C.
  • ethylene glycol (boiling point 197 ° C., divalent), 1,4-butanediol (boiling point 230 ° C., divalent), 1,6-hexanediol (boiling point 250 ° C., Dimethyl), trimethylolpropane (boiling point 250 ° C. or higher, trivalent), and the like.
  • trimethylolpropane is particularly preferable.
  • the composition for forming a conductive film of the present invention may contain fine particles of a Group 8-10 heavy metal element and / or a salt of a Group 8-10 heavy metal element.
  • fine particles and / or salts containing at least one metal element selected from the group consisting of groups 8 to 10 of the periodic table may be included.
  • Fine particles of Group 8-10 heavy metal elements include iron (Fe), cobalt (Co), nickel (Ni), rubidium (Ru), rhodium ( Rh), palladium (Pd), osmium (Os), iridium (Ir), fine particles made of a group 8-10 heavy metal element such as platinum (Pt) or an alloy.
  • the alloy include ruthenium-platinum alloy and silver-palladium alloy.
  • the heavy metal fine particles fine particles of palladium or platinum are preferable.
  • the size of the heavy metal fine particles is not particularly limited, but is preferably 1 nm to 50 nm, and more preferably 1 nm to 10 nm. By using heavy metal fine particles having a small particle diameter, the surface area is increased and the activity of the copper oxide reduction reaction is improved.
  • Group 8-10 heavy metal element salt Specific examples of salts of Group 8-10 heavy metal elements (hereinafter sometimes referred to as “heavy metal salts”) include ruthenium trichloride, ruthenium tribromide, rhodium trichloride, iridium trichloride, sodium hexachloroiridate, Palladium dichloride, potassium tetrachloroparadate, platinum dichloride, potassium tetrachloroplatinate, halide salts such as nickel dichloride, iron trichloride, cobalt trichloride, acetates such as ruthenium acetate, rhodium acetate, palladium acetate, Ruthenium trifluoroacetate, rhodium trifluoroacetate, palladium trifluoroacetate, etc., sulfates such as ferrous sulfate, ruthenium nitrate, rhodium nitrate, cobalt
  • Oxide, tri (acetylacetonato) ruthenium, di (acetylacetonato) can be exemplified nickel, di (acetylacetonato) acetylacetonate salts such as palladium or the like. Of these, palladium or platinum salts are preferred.
  • the composition for forming a conductive film of the present invention may contain a polymer compound.
  • Polymer compounds include poly-N-vinyl compounds such as polyvinyl pyrrolidone and polyvinyl caprolactone, polyurethanes, cellulose compounds and derivatives thereof, epoxy compounds, polyester compounds, chlorinated polyolefins, thermoplastic resins such as polyacryl compounds, heat A curable resin can be used. These polymer compounds have different effects, but all have a function as a binder and a function as a reducing agent. Among these, polyvinylpyrrolidone is preferable because it has a good balance between the binder effect and the reducing agent effect.
  • the composition for forming a conductive film of the present invention may contain a solvent.
  • the solvent include methanol, ethanol, propanol, 2-propanol, allyl alcohol, butanol, 2-butanol, pentanol, 2-pentanol, 3-pentanol, cyclopentanol, hexanol, 2-hexanol, 3- Alcohol solvents such as hexanol, cyclohexanol, ether solvents such as diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxane, triglyme, tetraglyme, methyl acetate, butyl acetate, benzyl benzoate , Ester solvents such as dimethyl carbonate, ethylene carbonate, ⁇ -butyrolactone, caprolactone, benzene
  • a solvent can be used individually by 1 type or in combination of 2 or more types.
  • the solvent those having a boiling point of less than 180 ° C. are preferable. This is because the solvent can be sufficiently removed from the composition for forming a conductive film by applying the composition for forming a conductive film on a substrate, followed by drying, heating, or light irradiation.
  • water, an alcohol solvent, an amide solvent or a mixed solvent of two or more of these are preferable, and water and alcohol having a boiling point of less than 180 ° C. are preferable because the dispersibility of the cupric oxide nanoparticles is good.
  • a mixed solvent with a system solvent is preferred.
  • the conductive film-forming composition of the present invention may contain other components.
  • the conductive film forming composition may contain a surfactant.
  • Surfactant plays the role which improves the dispersibility of a cupric oxide nanoparticle.
  • the type of the surfactant is not particularly limited, and examples thereof include an anionic surfactant, a cationic surfactant, a nonionic surfactant, a fluorine surfactant, and an amphoteric surfactant. These surfactants can be used alone or in combination of two or more.
  • the conductive film-forming composition of the present invention comprises cupric oxide nanoparticles, an alcohol compound, optionally heavy metal fine particles and / or heavy metal salts, optionally a polymer compound, optionally a solvent, and optionally other It can be produced by mixing the ingredients.
  • the electrical conductivity of the composition for forming a conductive film of the present invention is 2 to 240 mS / m, preferably 2 to 130 mS / m, more preferably 2 to 50 mS / m. Within this range, the substrate adhesion and conductivity of the conductive film will be more excellent.
  • cupric oxide nanoparticles are usually handled in the state of a dispersion dispersed in a dispersion medium such as water, alcohol, or a mixture thereof, but nitrate ions that are impurities when cupric oxide nanoparticles are synthesized. It is desirable to remove sodium ions as much as possible.
  • a method for removing nitrate ions and sodium ions for example, the operation of precipitating cupric oxide nanoparticles by centrifugation, replacing the dispersion medium with one not containing these ions, and redispersing is preferably performed once or more. Is a method of repeating 2 times or more, more preferably 3 times or more.
  • the content of the alcohol compound in the composition for forming a conductive film of the present invention is 20 to 1000 parts by weight, preferably 50 to 500 parts by weight, and preferably 50 to 300 parts by weight with respect to 100 parts by weight of cupric oxide nanoparticles. Part by mass is more preferable. Within this range, at least one of the substrate adhesion and conductivity of the conductive film is more excellent.
  • the total content of heavy metal fine particles and heavy metal salt in the composition for forming a conductive film of the present invention is not particularly limited, but is preferably 0.005 to 50 parts by mass with respect to 100 parts by mass of cupric oxide nanoparticles. 0.01 to 10 parts by mass is more preferable, 0.05 to 10 parts by mass is further preferable, 0.1 to 10 parts by mass is still more preferable, 0.5 to 10 parts by mass is still more preferable, and 0.5 to 10 parts by mass is preferable. 5 parts by mass is even more preferable. Within this range, at least one of the substrate adhesion and conductivity of the conductive film is further improved.
  • composition for electrically conductive film formation of this invention contains a high molecular compound
  • content in the composition for electrically conductive film formation is although it does not specifically limit, It is 0.00 with respect to 100 mass parts of cupric oxide nanoparticles. 001 to 5 parts by mass is preferable, 0.001 to 3 parts by mass is more preferable, 0.001 to 1 part by mass is further preferable, and 0.001 to 0.1 part by mass is even more preferable. Within this range, at least one of the substrate adhesion and conductivity of the conductive film is further improved.
  • the content in the composition for forming a conductive film of the present invention is not particularly limited, but is 1 to 10,000 parts by mass with respect to 100 parts by mass of cupric oxide nanoparticles. Is preferably 10 to 1000 parts by mass, more preferably 10 to 500 parts by mass.
  • the viscosity of the conductive film forming composition is preferably adjusted to a viscosity suitable for printing applications such as inkjet and screen printing.
  • a viscosity suitable for printing applications such as inkjet and screen printing.
  • inkjet discharge 1 to 50 cP is preferable, and 1 to 40 cP is more preferable.
  • screen printing it is preferably from 1,000 to 100,000 cP, more preferably from 10,000 to 80,000 cP.
  • the method for preparing the conductive film forming composition is not particularly limited, and a known method can be adopted.
  • cupric oxide nanoparticles (dispersion), an alcohol compound, optionally heavy metal fine particles and / or heavy metal salts, optionally a polymer compound, optionally a solvent, and optionally other components were added.
  • the composition can be obtained by dispersing the components by a known means such as an ultrasonic method (for example, treatment with an ultrasonic homogenizer), a mixer method, a three-roll method, or a ball mill method.
  • the method for producing a conductive film on a substrate using the composition for forming a conductive film of the present invention comprises at least a coating film forming step and a sintering step. Furthermore, if desired, a drying step may be provided.
  • a coating-film formation process is a process of providing the composition for electrically conductive film formation of this invention on a base material, and forming a coating film. By this step, a coating film before being subjected to the sintering treatment in the sintering step is obtained. You may perform the drying process which dries the coating film provided on the base material before performing a sintering process.
  • a well-known thing can be used as a base material used at this process.
  • the material used for the substrate include resin, paper, glass, silicon-based semiconductor, compound semiconductor, metal oxide, metal nitride, wood, or a composite thereof. More specifically, low density polyethylene resin, high density polyethylene resin, ABS resin, acrylic resin, styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene) Resin base materials such as terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN)), polyacetal resin, polysulfone resin, polyetherimide resin, polyetherketone resin, polyimide resin, cellulose derivative; Uncoated printing paper, finely coated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), unbleached wrapping paper (double kraft paper for heavy bags, bilateral Kraft paper), bleached wrapping
  • the method for applying the conductive film forming composition onto the substrate is not particularly limited, and a known method can be adopted.
  • coating methods such as a screen printing method, a dip coating method, a spray coating method, a spin coating method, and an ink jet method can be used.
  • the shape of application is not particularly limited, and may be a surface covering the entire surface of the substrate or a pattern (for example, a wiring or a dot).
  • the coating amount of the composition for forming a conductive film on the substrate may be appropriately adjusted according to the desired film thickness of the conductive film.
  • the film thickness (thickness) of the coating film is 0.01 to 1000 ⁇ m. Is preferable, 0.1 to 100 ⁇ m is more preferable, 0.1 to 50 ⁇ m is more preferable, and 1 to 30 ⁇ m is even more preferable.
  • This step is a step of performing drying treatment on the formed coating film and removing at least a part of the solvent contained in the composition for forming a conductive film. If desired, this step can be performed after the above-described coating film forming step and before the sintering step described later.
  • the generation of minute cracks and voids due to the vaporization and expansion of the solvent can be suppressed in the sintering step described later. This is preferable in terms of adhesion between the film and the substrate.
  • the drying treatment can be performed by heating using a warm air dryer or the like, and the drying temperature is preferably 50 ° C. or higher and lower than 100 ° C., more preferably 70 to 90 ° C.
  • the drying treatment may be performed in either a non-oxidizing atmosphere or an oxidizing atmosphere.
  • the non-oxidizing atmosphere include an inert gas atmosphere such as nitrogen and argon, and a reducing gas atmosphere such as hydrogen.
  • the oxidizing atmosphere include an air atmosphere and an oxygen atmosphere.
  • This step is a step in which a conductive film is formed by performing a heat treatment and / or a light irradiation treatment on the coating film formed on the substrate (or the dried coating film when the drying process is performed).
  • a heat treatment and / or a light irradiation treatment By performing the heat treatment and / or the light irradiation treatment, the copper oxide of the cupric oxide nanoparticles is reduced to produce metallic copper, and the reduction of the produced metallic copper particles and metallic silver particles can be performed. Promoted to form a metal conductor in the metal conductive film.
  • the heating temperature is not particularly limited in that a conductive film having better conductivity can be formed in a short time, but the heating temperature is preferably 110 to 180 ° C., more preferably 110 to 150 ° C.
  • the heating time is preferably 5 to 120 minutes, more preferably 5 to 30 minutes.
  • the heating means is not particularly limited, and known heating means such as an oven and a hot plate can be used.
  • the conductive film can be formed by heat treatment at a relatively low temperature, and therefore, the process cost is low.
  • the light irradiation treatment can reduce and sinter to metallic copper by irradiating light on the portion to which the coating film is applied at room temperature for a short time, and heating for a long time.
  • the base material is not deteriorated by, and the adhesion of the conductive film to the base material becomes better.
  • the light source used in the light irradiation treatment is not particularly limited, and examples thereof include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays.
  • g-line, i-line, deep-UV light, and high-density energy beam are used.
  • Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
  • the light irradiation is preferably light irradiation with a flash lamp, and more preferably pulsed light irradiation with a flash lamp. Irradiation with high-energy pulsed light can concentrate and heat the surface of the portion to which the coating film has been applied in a very short time, so that the influence of heat on the substrate can be extremely reduced.
  • the irradiation energy of the pulse light is preferably 1 ⁇ 100J / cm 2, more preferably 1 ⁇ 30J / cm 2, preferably from 1 ⁇ sec ⁇ 100 m sec as a pulse width, and more preferably 10 ⁇ sec ⁇ 10 m sec.
  • the irradiation time of the pulsed light is preferably 1 to 100 milliseconds, more preferably 1 to 50 milliseconds, and further preferably 1 to 20 milliseconds.
  • the cupric oxide nanoparticle absorbs light and works as a photothermal conversion substance that converts it into heat, and plays a role of transferring heat into the coating film.
  • the above heat treatment and light irradiation treatment may be performed alone or both may be performed simultaneously. Moreover, after performing one process, you may perform the other process further.
  • the heat treatment and the light irradiation treatment may be performed in either a non-oxidizing atmosphere or an oxidizing atmosphere.
  • the non-oxidizing atmosphere include an inert gas atmosphere such as nitrogen and argon, and a reducing gas atmosphere such as hydrogen.
  • the oxidizing atmosphere include an air atmosphere and an oxygen atmosphere.
  • a conductive film containing a metal conductor substantially made of metallic copper is produced.
  • the film thickness (thickness) of the conductive film is not particularly limited, and an optimum film thickness is appropriately selected according to the application used. For example, 10 to 1000 nm is preferable, 10 to 500 nm is more preferable, 20 to 200 nm is more preferable, and 50 to 150 nm is even more preferable from the viewpoint of organic thin film transistor electrode use.
  • the film thickness is a value (average value) obtained by measuring three or more thicknesses at arbitrary points on the conductive film and arithmetically averaging the values.
  • the conductive film may be provided on the entire surface of the base material or in a pattern.
  • the patterned conductive film is useful as a conductor wiring (wiring) such as a printed wiring board.
  • wiring conductor wiring
  • the above-mentioned composition for forming a conductive film was applied to a substrate in a pattern, and the above heat treatment and / or light irradiation treatment was performed, or the entire surface of the substrate was provided.
  • a method of etching the conductive film in a pattern may be used.
  • the etching method is not particularly limited, and a known subtractive method, semi-additive method, or the like can be employed.
  • an insulating layer (insulating resin layer, interlayer insulating film, solder resist) is further laminated on the surface of the patterned conductive film, and further wiring (metal) is formed on the surface. Pattern) may be formed.
  • the material of the insulating film is not particularly limited.
  • epoxy resin glass epoxy resin, aramid resin, crystalline polyolefin resin, amorphous polyolefin resin, fluorine-containing resin (polytetrafluoroethylene, perfluorinated polyimide, perfluorinated) Amorphous resin), polyimide resin, polyether sulfone resin, polyphenylene sulfide resin, polyether ether ketone resin, liquid crystal resin, and the like.
  • an epoxy resin, a polyimide resin, or a liquid crystal resin and more preferably an epoxy resin. Specific examples include ABF GX-13 manufactured by Ajinomoto Fine Techno Co., Ltd.
  • solder resist which is a kind of insulating layer material used for wiring protection, is described in detail in, for example, Japanese Patent Application Laid-Open No. 10-204150 and Japanese Patent Application Laid-Open No. 2003-222993. These materials can also be applied to the present invention if desired.
  • solder resist commercially available products may be used. Specific examples include PFR800 manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR4000 (trade name), SR7200G manufactured by Hitachi Chemical Co., Ltd., and the like.
  • the base material (base material with a conductive film) having the conductive film obtained above can be used for various applications.
  • a printed wiring board, TFT, FPC, RFID, etc. are mentioned.
  • Table 1 shows the granulation materials, granulation raw materials, reaction conditions, and purification methods used in Synthesis Examples 1-18.
  • cupric oxide dispersion liquid zirconia beads having the same mass as the dispersoid were added, and stirred and dispersed with Awatori Rentaro for 3 minutes to obtain a cupric oxide nanoparticle dispersion liquid.
  • XRD analysis strong diffraction peaks derived from the (002) and (111) planes were observed near 35.5 ° and 38 °, respectively, and it was confirmed that the obtained nanoparticles were cupric oxide.
  • cupric oxide nanoparticles 1 As a result of TEM observation, the average primary particle size of the obtained cupric oxide nanoparticles was 5 nm, the average aspect ratio was 1.5, and the proportion of particles having a primary particle size of 30 m or more was 2%. Met.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 1”.
  • cupric oxide nanoparticles 2 As a result of TEM observation, the average primary particle diameter of the obtained cupric oxide nanoparticles was 3 nm, the average aspect ratio was 1.5, and the ratio of particles having a primary particle diameter of 30 nm or more was 5%. Was less than.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 2”.
  • cupric oxide nanoparticles 3 As a result of TEM observation, the average primary particle diameter of the obtained cupric oxide nanoparticles was 8 nm, the average aspect ratio was 1.5, and the ratio of particles having a primary particle diameter of 30 nm or more was 5%. Was less than.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 3”.
  • cupric oxide nanoparticles 4 It was synthesized in the same manner as cupric oxide nanoparticle 1 except that a mixed solvent (100 mL) in which ethylene glycol and water were mixed at a volume ratio of 1: 1 was used instead of ethylene glycol (100 mL). A cupric nanoparticle dispersion was obtained. By XRD analysis, it was confirmed that the obtained nanoparticles were cupric oxide. As a result of TEM observation, the average primary particle size of the obtained cupric oxide nanoparticles was 9 nm, the average aspect ratio was 2.3, and the proportion of particles having a primary particle size of 30 nm or more was 5%. Was less than. The cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 4”.
  • cupric oxide nanoparticle dispersion was obtained by synthesizing in the same manner as cupric oxide nanoparticle 1 except that water (100 mL) was used instead of ethylene glycol (100 mL). By XRD analysis, it was confirmed that the obtained nanoparticles were cupric oxide. As a result of TEM observation, the average primary particle size of the obtained cupric oxide nanoparticles was 17 nm, the average aspect ratio was 3.8, and the proportion of particles having a primary particle size of 30 nm or more was 15%. Was less than.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 5”.
  • cupric oxide nanoparticles 6 As a result of TEM observation, the average primary particle size of the obtained cupric oxide nanoparticles was 24 nm, the average aspect ratio was 4.8, and the proportion of particles having a primary particle size of 30 nm or more was 20%. Was less than.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 6”.
  • cupric oxide nanoparticles 7 The reaction conditions were synthesized in the same manner as cupric oxide nanoparticles 1 except that the reaction conditions were changed from heating at 90 ° C. for 10 minutes to heating at 100 ° C. for 10 minutes to obtain a cupric oxide nanoparticle dispersion. It was. By XRD analysis, it was confirmed that the obtained nanoparticles were cupric oxide. As a result of TEM observation, the average primary particle diameter of the obtained cupric oxide nanoparticles was 4 nm, the average aspect ratio was 1.5, and the ratio of particles having a primary particle diameter of 30 nm or more was 5%. Was less than. The cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 7”.
  • cupric oxide nanoparticles 8 As a result of TEM observation, the average primary particle size of the obtained cupric oxide nanoparticles was 8 nm, the average aspect ratio was 2.0, and the proportion of particles having a primary particle size of 30 nm or more was 10%. Was less than.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 8”.
  • cupric oxide nanoparticles 9 the average primary particle diameter of the obtained cupric oxide nanoparticles was 15 nm, the average aspect ratio was 2.4, and the ratio of particles having a primary particle diameter of 30 nm or more was 30%. Was less than.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 9”.
  • cupric oxide nanoparticle dispersion was obtained by synthesizing in the same manner as cupric oxide nanoparticles 1 except that the number of repetitions of centrifugation at 20000 ⁇ G for 30 minutes was changed from 3 to 2 times. It was. By XRD analysis, it was confirmed that the obtained nanoparticles were cupric oxide. As a result of TEM observation, the average primary particle diameter of the obtained cupric oxide nanoparticles was 5 nm, the average aspect ratio was 1.5, and the ratio of particles having a primary particle diameter of 30 nm or more was 5%. Was less than.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 10”.
  • cupric oxide nanoparticle dispersion was obtained by synthesizing in the same manner as cupric oxide nanoparticle 1 except that the number of repetitions of centrifugation at 20000 ⁇ G for 30 minutes was changed from 3 to 1. It was. By XRD analysis, it was confirmed that the obtained nanoparticles were cupric oxide. As a result of TEM observation, the average primary particle diameter of the obtained cupric oxide nanoparticles was 5 nm, the average aspect ratio was 1.5, and the ratio of particles having a primary particle diameter of 30 nm or more was 5%. Was less than.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 11”.
  • cupric oxide nanoparticle dispersion was synthesized in the same manner as cupric oxide nanoparticles 1 except that centrifugation at 20000 ⁇ G for 30 minutes was changed to centrifugation at 5000 ⁇ G for 30 minutes. Got. By XRD analysis, it was confirmed that the obtained nanoparticles were cupric oxide. As a result of TEM observation, the average primary particle diameter of the obtained cupric oxide nanoparticles was 5 nm, the average aspect ratio was 1.5, and the ratio of particles having a primary particle diameter of 30 nm or more was 5%. Was less than.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 12”.
  • cupric oxide nanoparticles 13 As a result of TEM observation, the average primary particle diameter of the obtained cupric oxide nanoparticles was 49 nm, the average aspect ratio was 1.5, and the ratio of particles having a primary particle diameter of 30 nm or more was 90%. It was super.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 13”.
  • cupric oxide nanoparticles 14 As a result of TEM observation, the average primary particle diameter of the obtained cupric oxide nanoparticles was 30 nm, the average aspect ratio was 1.5, and the proportion of particles having a primary particle diameter of 30 nm or more was 40%. Met.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 14”.
  • cupric oxide nanoparticles 16 As a result of TEM observation, the average primary particle size of the obtained cupric oxide nanoparticles was 15 nm, the average aspect ratio was 8.0, and the proportion of particles having a primary particle size of 30 nm or more was 20%. Met.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 16”.
  • cupric oxide nanoparticle dispersion was obtained by synthesizing in the same manner as cupric oxide nanoparticles 1 except that no centrifugation was performed at 20000 ⁇ g for 30 minutes.
  • XRD analysis it was confirmed that the obtained nanoparticles were cupric oxide.
  • the average primary particle diameter of the obtained cupric oxide nanoparticles was 5 nm, the average aspect ratio was 1.5, and the ratio of particles having a primary particle diameter of 30 nm or more was 5%. Was less than.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 17”.
  • cupric oxide nanoparticle dispersion was obtained by synthesizing in the same manner as cupric oxide nanoparticle 1 except that the number of repetitions of centrifugation at 20000 ⁇ G for 30 minutes was changed from 3 to 10 times. It was. By XRD analysis, it was confirmed that the obtained nanoparticles were cupric oxide. As a result of TEM observation, the average primary particle diameter of the obtained cupric oxide nanoparticles was 5 nm, the average aspect ratio was 1.5, and the ratio of particles having a primary particle diameter of 30 nm or more was 5%. Was less than.
  • the cupric oxide nanoparticles thus obtained are hereinafter referred to as “cupric oxide nanoparticles 18”.
  • Example 1 ⁇ Preparation of composition for forming conductive film> Cupric oxide nanoparticles 1 (obtained in Synthesis Example 1, 100 parts by mass), trimethylolpropane (Tokyo Chemical Industry Co., Ltd., 200 parts by mass), palladium acetate (Tokyo Chemical Industry Co., Ltd., 1 part by mass) ) And the mixture was processed for 5 minutes with a rotation and revolution mixer (made by THINKY, manufactured by Awatori Nertaro ARE-310) to obtain a composition for forming a conductive film.
  • Table 2 shows each component of the composition for forming a conductive film and its content.
  • composition 1 for forming a conductive film The electrical conductivity of the obtained composition for forming a conductive film was measured with an electrical conductivity meter (CM-30R, manufactured by Toa DK Corporation). The electric conductivity [mS / m] is shown in the electric conductivity column of Table 2.
  • this composition for forming a conductive film is referred to as “Composition 1 for forming a conductive film”.
  • the evaluation criteria are as follows. In practice, it is preferably 3 or more. “5”: Adhesion of the conductive film is not observed on the tape, and peeling at the interface between the conductive film and the substrate is not observed. “4”: The conductive film is slightly attached to the tape, but peeling at the interface between the conductive film and the substrate is not observed.
  • volume resistivity About the obtained electrically conductive film, volume resistivity was measured using the four-probe method resistivity meter, and electroconductivity was evaluated. The evaluation criteria are as follows. “5”: Volume resistivity is less than 50 ⁇ ⁇ cm “4”: Volume resistivity is 50 ⁇ ⁇ cm or more and less than 100 ⁇ ⁇ cm “3”: Volume resistivity is 100 ⁇ ⁇ cm or more and less than 300 ⁇ ⁇ cm “2”: Volume resistance Rate is 300 ⁇ ⁇ cm or more and less than 1000 ⁇ ⁇ cm “1”: Volume resistivity is 1000 ⁇ ⁇ cm or more
  • Example 2 to 9 cupric oxide nanoparticles were used in place of cupric oxide nanoparticles 1 (Example 1), except that cupric oxide nanoparticles 2 to 9 were used, respectively.
  • a conductive film forming composition was prepared in the same manner as in Example 1, a conductive film was formed, and the conductive film was evaluated. The evaluation results of the substrate adhesion and the conductivity are shown in Table 2.
  • Example 10 to 13 the content of the alcohol compound (trimethylolpropane) was changed from 200 parts by mass (Example 1) to 50 parts by mass (Example 10), 500 parts by mass (Example 11), and 1000 parts by mass. Except for the point changed to (Example 12) or 2000 parts by mass (Example 13), a conductive film-forming composition was prepared in the same manner as in Example 1, a conductive film was formed, and the conductive film was evaluated. . The evaluation results of the substrate adhesion and the conductivity are shown in Table 2.
  • Example 14 to 19 In Examples 14 to 19, the content of the fine particles of Group 8 to 10 heavy metal element or heavy metal salt (palladium acetate) was changed from 1 part by weight (Example 1) to 5 parts by weight (Example 14), 10 parts by weight.
  • Example 15 20 parts by mass (Example 16), 0.5 parts by mass (Example 17), 0.05 parts by mass (Example 18) or 0.008 parts by mass (Example 19)
  • the electrical conductivity of the composition for forming a conductive film is 17 mS / m (Example 14), 26 mS / m (Example 15), 32 mS / m (Example 16), 8 mS / m (Example 17), Except for the point being 6 mS / m (Example 18) or 5 mS / m (Example 19), a conductive film-forming composition was prepared in the same manner as in Example 1 to form a conductive film. evaluated. The evaluation results of the substrate adhesion and the conductivity are shown in Table 2.
  • Examples 20-24 do not contain fine particles or heavy metal salts of Group 8-10 heavy metal elements (Example 20), or palladium acetate (Example 1) as fine particles or salts of Group 8-10 heavy metal elements. Instead, palladium trifluoroacetate (Example 21), palladium fine particles (Example 22), platinum fine particles (Example 23) or ruthenium fine particles (Example 24) were used, and the electrical properties of the conductive film forming composition A conductive film forming composition was prepared in the same manner as in Example 1 except that the conductivity was 4 mS / m (Example 20) and 5 mS / m (Examples 22 to 24), and a conductive film was formed. The conductive film was evaluated. The evaluation results of the substrate adhesion and the conductivity are shown in Table 2.
  • Example 25 instead of trimethylolpropane (Example 1) as an alcohol compound, ethylene glycol (Example 25), 1,4-butanediol (Example 26) or 1,6-hexanediol (A composition for forming a conductive film was prepared in the same manner as in Example 1 except that Example 27) was used, a conductive film was formed, and the conductive film was evaluated. The evaluation results of the substrate adhesion and the conductivity are shown in Table 2.
  • cupric oxide nanoparticles 10 (Example 28), cupric oxide nanoparticles instead of cupric oxide nanoparticles 1 (Example 1) 11 (Example 29) or cupric oxide nanoparticles 12 (Example 30), and the electrical conductivity of the composition for forming a conductive film was 46 mS / m (Example 28), 122 mS / m (Example) Except for the point of Example 29) or 240 mS / m, the composition for electrically conductive film formation was prepared like Example 1, the electrically conductive film was formed, and the electrically conductive film was evaluated. The evaluation results of the substrate adhesion and the conductivity are shown in Table 2.
  • Example 31 to 33 cupric oxide nanoparticles were used in place of cupric oxide nanoparticles 1 (Example 1) as cupric oxide nanoparticles, and polyvinylpyrrolidone was used as the polymer compound.
  • the electrical conductivity of the composition for forming a conductive film is 38 mS / m (Implementation)
  • a conductive film-forming composition was prepared, a conductive film was formed, and the conductive film was evaluated in the same manner as in Example 1, except that it was Example 31, 32) or 49 mS / m (Example 33). .
  • the evaluation results of the substrate adhesion and the conductivity are shown in Table 2.
  • Comparative Examples 1 to 4 Comparative Examples 1 to 4 except that cupric oxide nanoparticles 13 to 16 (Comparative Examples 1 to 4 respectively) were used instead of cupric oxide nanoparticles 1 as cupric oxide nanoparticles. Then, in the same manner as in Example 1, a composition for forming a conductive film was prepared, a conductive film was formed, and the conductive film was evaluated. The evaluation results of the substrate adhesion and the conductivity are shown in Table 2.
  • Comparative Example 5 In Comparative Example 5, cupric oxide nanoparticles were used in place of cupric oxide nanoparticles 1 as cupric oxide nanoparticles, and the electrical conductivity of the conductive film forming composition was 1200 mS / Except for the point being m, a conductive film-forming composition was prepared in the same manner as in Example 1, a conductive film was formed, and the conductive film was evaluated. The evaluation results of the substrate adhesion and the conductivity are shown in Table 2.
  • Comparative Example 6 In Comparative Example 6, as the cupric oxide nanoparticles, instead of cupric oxide nanoparticles 1, cupric oxide nanoparticles 18 were used, palladium acetate was not contained, and a conductive film forming composition. A conductive film-forming composition was prepared, a conductive film was formed, and the conductive film was evaluated in the same manner as in Example 1, except that the electrical conductivity was 1 mS / m. The evaluation results of the substrate adhesion and the conductivity are shown in Table 2.
  • A, B, C and D represent the following components, respectively.
  • Example 9 In which the proportion of particles having a primary particle diameter of more than 30 nm is less than 30% and Example 6 in which the ratio of particles is less than 20% is evaluated as “Evaluation of substrate adhesion of conductive film” 4 ”and the evaluation of conductivity was“ 3 ”, which met the practical requirement level.
  • Example 5 In Example 5 in which the ratio of the particles having a primary particle diameter exceeding 30 nm among cupric oxide nanoparticles is less than 15%, both the base material adhesion and the conductive evaluation of the conductive film are “4”, The conductivity was superior to Examples 6 and 9.
  • Example 8 in which the ratio of particles having a primary particle diameter exceeding 30 nm among cupric oxide nanoparticles is less than 10%, the evaluation of the substrate adhesion of the conductive film was “5”, and the evaluation of conductivity was “ 4 ”, the substrate adhesion and conductivity were superior to those of Examples 6 and 9, and the substrate adhesion was superior to that of Example 5.
  • Examples 1 to 4 and 7 in which the ratio of the particles having a primary particle diameter exceeding 30 nm in the cupric oxide nanoparticles is less than 5% both the base material adhesion and the conductive evaluation of the conductive film were evaluated as “5. It was particularly excellent.
  • Example 13 In Example 13 in which the content of the alcohol compound is 2000 parts by mass with respect to 100 parts by mass of the cupric oxide nanoparticles, the evaluation of the substrate adhesion of the conductive film is “3”, and the evaluation of the conductivity is “4”. And met practical requirements.
  • Example 12 In Example 12 in which the content of the alcohol compound is 1000 parts by mass with respect to 100 parts by mass of cupric oxide nanoparticles, the base material adhesion and conductivity evaluation of the conductive film are both “4”. Compared to 13, the substrate adhesion was excellent.
  • Example 11 in which the content of the alcohol compound is 500 parts by mass with respect to 100 parts by mass of the cupric oxide nanoparticles, the evaluation of the adhesion of the conductive film to the base material is “4”, and the evaluation of the conductivity is “5”.
  • the substrate adhesion and conductivity were excellent compared to Example 13, and the conductivity was excellent compared to Example 12.
  • Example 1 in which the content of the alcohol compound is 50 parts by mass with respect to 100 parts by mass of cupric oxide nanoparticles and 200 parts by mass, the base material adhesion and conductivity of the conductive film are evaluated. Both were “5” and were particularly excellent.
  • Example 19 in which the total content of the heavy metal fine particles and the heavy metal salt is 0.008 parts by mass with respect to 100 parts by mass of cupric oxide nanoparticles is 20 parts by mass, and the base material adhesion of the conductive film is The evaluation of the property was “4” and the evaluation of the conductivity was “3”, which met the practical requirement level.
  • Example 18 in which the total content of the heavy metal fine particles and the heavy metal salt was 0.05 parts by mass with respect to 100 parts by mass of the cupric oxide nanoparticles, both the base material adhesion of the conductive film and the evaluation of the conductivity were “ 4 ”and the conductivity was superior to those of Examples 16 and 19.
  • Example 15 in which the total content of the heavy metal fine particles and the heavy metal salt was 10 parts by mass with respect to 100 parts by mass of the cupric oxide nanoparticle, The evaluation was “5”, and the conductivity was superior to those of Examples 16, 18 and 19.
  • Example 17 in which the total content of the heavy metal fine particles and the heavy metal salt is 0.5 parts by mass with respect to 100 parts by mass of cupric oxide nanoparticles, Example 1 that is 1 part by mass, and implementation that is 5 parts by mass
  • Example 14 the base material adhesion and conductivity evaluation of the conductive film were both “5”, which was particularly excellent.
  • Example 20 which did not contain heavy metal fine particles and / or heavy metal salt, the substrate adhesion and conductivity evaluation of the conductive film were both “3”, reaching the practical requirement level.
  • Example 24 including the ruthenium fine particles as the heavy metal fine particles and / or the heavy metal salt both the base material adhesion and the conductive evaluation of the conductive film were “3”, and the practical requirement level was reached.
  • Example 23 containing platinum fine particles as heavy metal fine particles and / or heavy metal salts the substrate adhesion evaluation of the conductive film was “3”, and the conductivity evaluation was “4”, compared with Examples 20 and 24. The conductivity was excellent.
  • Example 22 containing palladium fine particles as heavy metal fine particles and / or heavy metal salt is both “4” in the evaluation of the adhesion of the conductive film to the base material and the conductivity, which is superior to Examples 20 and 24, Compared with Example 23, the substrate adhesion was excellent.
  • Example 21 containing heavy metal fine particles and / or palladium trifluoroacetate as a heavy metal salt the evaluation of the adhesion of the conductive film to the substrate was “5” and the evaluation of conductivity was “4”. The substrate adhesion was superior, and the substrate adhesion and conductivity were superior to Examples 20 and 23.
  • Example 1 containing heavy metal fine particles and / or palladium acetate as a heavy metal salt both the base material adhesion and the conductive evaluation of the conductive film were “5”, which was particularly excellent.
  • Example 25 containing ethylene glycol (boiling point 197 ° C.) as the alcohol compound, the base material adhesion and the conductive evaluation of the conductive film were both “3”, and the practical requirement level was reached.
  • Example 26 containing 1,4-butanediol (boiling point 230 ° C.) as the alcohol compound, the evaluation of the adhesion of the conductive film to the substrate was “3”, and the evaluation of conductivity was “4”.
  • Example 27 containing 1,6-hexanediol (boiling point 250 ° C.) as an alcohol compound and Example 1 containing trimethylolpropane (boiling point 250 ° C. or more), both the adhesion of the conductive film to the base material and the evaluation of the conductive property were obtained. “5”, which was particularly excellent.
  • Example 30 in which the electrical conductivity of the composition for forming a conductive film was 240 mS / m, both the base material adhesion and the conductive evaluation of the conductive film were “3”, and the practical requirements were reached. .
  • Example 29 in which the electrical conductivity of the composition for forming a conductive film is 122 mS / m, both the base material adhesion and the conductive evaluation of the conductive film are “4”. Both conductivity and conductivity were excellent.
  • Example 30 in which the electrical conductivity of the composition for forming a conductive film is 46 mS / m and Example 1 in which the electrical conductivity is 10 mS / m are “5” for both the base material adhesion and the conductive evaluation of the conductive film, Especially excellent.
  • Example 33 containing 5 parts by mass of the polymer compound with respect to 100 parts by mass of cupric oxide nanoparticles, both the base material adhesion and the electrical conductivity of the conductive film were evaluated as “3”. Had reached.
  • Example 32 containing 1 part by mass of the polymer compound with respect to 100 parts by mass of cupric oxide nanoparticles, the base material adhesion evaluation of the conductive film was “4”, and the conductivity evaluation was “5”. Compared with Example 33, both substrate adhesion and conductivity were excellent.
  • Example 31 containing 0.1 part by mass of the polymer compound with respect to 100 parts by mass of cupric oxide nanoparticles and Example 1 not containing the polymer compound, the base material adhesion and conductivity of the conductive film were evaluated. Both were “5” and were particularly excellent.

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Abstract

Cette invention concerne une composition qui est capable de former un film conducteur ayant une excellente adhérence au substrat et d'excellentes propriétés conductrices, la composition comprenant des nanoparticules d'oxyde cuprique et un composé de type alcool, et étant caractérisée en ce que la teneur en composé de type alcool est de 20 à 1000 parties en poids pour 100 parties en poids de nanoparticules d'oxyde cuprique ; la taille de particule primaire moyenne des nanoparticules d'oxyde cuprique est de 3 à 25 nm ; le rapport d'aspect moyen des nanoparticules d'oxyde cuprique est de 1,1 à 5,0 (1,1 étant exclus) ; parmi les nanoparticules d'oxyde cuprique, la proportion de particules ayant une taille de particule primaire supérieure à 30 nm est inférieure à 30 % ; et la conductivité électrique de la composition destinée à former le film conducteur est 2 à 240 mS/m. Un procédé capable de former un film conducteur est également décrit, ledit procédé comprenant les étapes suivantes : une étape consistant à appliquer, sur un substrat de résine, la composition destinée à former un film précurseur du film conducteur sur le substrat en résine ; et une étape consistant à chauffer le film précurseur du film conducteur dans une atmosphère de gaz inerte à une température de 110 à 150°C pour former le film conducteur sur le substrat en résine.
PCT/JP2015/070059 2014-08-29 2015-07-13 Composition et procédé de formation d'un film conducteur WO2016031409A1 (fr)

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JP2004155638A (ja) * 2002-11-08 2004-06-03 Asahi Kasei Corp 金属酸化物分散体
JP2010135140A (ja) * 2008-12-03 2010-06-17 Fukuda Metal Foil & Powder Co Ltd 導電塗料用の片状金属微粉末及びその製造方法
JP2014067617A (ja) * 2012-09-26 2014-04-17 Fujifilm Corp 導電膜の製造方法および導電膜形成用組成物
JP2014116315A (ja) * 2007-05-18 2014-06-26 Applied Nanotech Holdings Inc 金属インク
JP2014148633A (ja) * 2013-02-04 2014-08-21 Fujifilm Corp 導電膜形成用組成物、導電膜の製造方法

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JP6018831B2 (ja) * 2011-08-05 2016-11-02 積水化学工業株式会社 接合構造体の製造方法

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JP2004155638A (ja) * 2002-11-08 2004-06-03 Asahi Kasei Corp 金属酸化物分散体
JP2014116315A (ja) * 2007-05-18 2014-06-26 Applied Nanotech Holdings Inc 金属インク
JP2010135140A (ja) * 2008-12-03 2010-06-17 Fukuda Metal Foil & Powder Co Ltd 導電塗料用の片状金属微粉末及びその製造方法
JP2014067617A (ja) * 2012-09-26 2014-04-17 Fujifilm Corp 導電膜の製造方法および導電膜形成用組成物
JP2014148633A (ja) * 2013-02-04 2014-08-21 Fujifilm Corp 導電膜形成用組成物、導電膜の製造方法

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