WO2015005046A1 - Composition de formation de film électriquement conducteur, procédé de production de film électriquement conducteur, et film électriquement conducteur - Google Patents

Composition de formation de film électriquement conducteur, procédé de production de film électriquement conducteur, et film électriquement conducteur Download PDF

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Publication number
WO2015005046A1
WO2015005046A1 PCT/JP2014/065346 JP2014065346W WO2015005046A1 WO 2015005046 A1 WO2015005046 A1 WO 2015005046A1 JP 2014065346 W JP2014065346 W JP 2014065346W WO 2015005046 A1 WO2015005046 A1 WO 2015005046A1
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Prior art keywords
conductive film
composition
copper
forming
copper oxide
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PCT/JP2014/065346
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English (en)
Japanese (ja)
Inventor
佑一 早田
悠史 本郷
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富士フイルム株式会社
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Publication of WO2015005046A1 publication Critical patent/WO2015005046A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0263—Details about a collection of particles
    • H05K2201/0272—Mixed conductive particles, i.e. using different conductive particles, e.g. differing in shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/08—Treatments involving gases
    • H05K2203/086—Using an inert gas
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods

Definitions

  • the present invention relates to a conductive film forming composition, a method for producing a conductive film, and a conductive film.
  • a dispersion of metal particles or metal oxide particles is applied to the base material by a printing method, and heat treatment is performed to sinter the conductive film or wiring on a circuit board.
  • a technique for forming an electrically conductive portion is known. Since the above method is simple, energy-saving, and resource-saving compared to conventional high-heat / vacuum process (sputtering) and plating process, it has high expectations in the development of next-generation electronics. In particular, in recent years, from the viewpoint of cost reduction, development of a method for forming a conductive film having excellent conductivity using a composition containing metal oxide particles is desired.
  • Patent Document 1 discloses a metal oxide dispersion containing copper oxide particles, metal powder, and sugar alcohol (claims).
  • the present inventors have examined a composition containing copper oxide particles, metal powder, and sugar alcohol with reference to Patent Document 1, and the conductivity and toughness of the resulting conductive film are recently required levels. It became clear that it does not necessarily satisfy. Therefore, in view of the above circumstances, the present invention provides a conductive film-forming composition capable of forming a conductive film having excellent conductivity and toughness, and production of a conductive film using the conductive film-forming composition. It is an object of the present invention to provide a method and a conductive film manufactured by the above manufacturing method.
  • the inventors of the present invention form a conductive film excellent in conductivity and toughness by blending copper oxide particles, copper particles, and sugars at a specific quantitative ratio. As a result, the present invention was completed. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • (1) Contains copper oxide particles (A) having an average particle size of 10 to 500 nm, copper particles (B) having an average particle size of 100 to 3000 nm, saccharides (C), water and / or a water-soluble solvent. and a solvent (D) contains at least, the content of the copper oxide particles (a) (W a) and the content of the copper particles (B) (W B) and the mass ratio of (W a: W B) is , 3: 1 to 1: 3, by weight of the total content of the copper oxide particles (a) and the copper particles (B) and (W AB) the content of the saccharide (C) and (W C) A composition for forming a conductive film, wherein the ratio (W AB : W C ) is 20: 1 to 2: 1.
  • sugar (C) is a monosaccharide.
  • a conductive film-forming composition capable of forming a conductive film having excellent conductivity and toughness, and production of a conductive film using the conductive film-forming composition.
  • the method and the conductive film manufactured by the above manufacturing method can be provided.
  • composition for forming a conductive film of the present invention comprises copper oxide particles (A) having an average particle diameter of 10 to 500 nm and copper having an average particle diameter of 100 to 3000 nm. It contains at least particles (B), saccharides (C), and a solvent (D) containing water and / or a water-soluble solvent.
  • the content of the copper oxide particles (A) (W A) and the content of the copper particles (B) (W B) and the mass ratio of (W A: W B) is 3: 1 to 1: 3 and the total content of the copper oxide particles (a) and the copper particles (B) (W AB) and the content of the saccharide (C) (W C) and the weight ratio of (W AB: W C ) Is 20: 1 to 2: 1.
  • the composition of the present invention takes such a configuration, the obtained conductive film is considered to be excellent in conductivity and toughness. This is not clear in detail, but is assumed to be as follows.
  • the composition of the present invention contains copper oxide particles, copper particles, and sugars.
  • the saccharide acts as a reducing agent and reduces the copper oxide particles.
  • the reactivity of the reduction reaction is greatly improved, and the copper oxide particles are reduced to copper in a short time.
  • copper oxide is reduced to copper, the copper oxide particles reduced to copper fuse the copper particles to form a conductive film.
  • saccharides are excellent in reducing power, the copper oxide particles are efficiently reduced and the copper particles are fused well.
  • the conductive film obtained from the composition of the present invention is considered to have excellent toughness.
  • composition of the present invention is also characterized in that the ratio of each component is specific. That is, since the quantity ratio between the copper oxide particles and the copper particles is specific, the reduction of the copper oxide particles proceeds uniformly throughout the system, and a conductive film in which the copper particles are well bonded is formed. It is thought that it leads to improvement of the property and toughness.
  • each component (copper oxide particle (A), copper particle (B), saccharide
  • the copper oxide particles (A) contained in the composition of the present invention are not particularly limited as long as they are particulate copper oxide having an average particle diameter of 10 to 500 nm.
  • the particulate form refers to a small granular form, and specific examples thereof include a spherical shape and an ellipsoidal shape. It does not have to be a perfect sphere or ellipsoid, and a part may be distorted.
  • the copper oxide particles (A) are preferably copper oxide (I) particles (Cu 2 O particles) or copper oxide (II) particles (CuO particles), and can be obtained at low cost. From the viewpoint of excellent properties and excellent reduction reactivity, copper (II) oxide particles are more preferable.
  • the average particle diameter of the copper oxide particles (A) is not particularly limited as long as it is in the range of 10 to 500 nm, but is preferably 50 to 300 nm, and more preferably 80 to 180 nm.
  • the average particle diameter in this invention points out an average primary particle diameter.
  • the average particle diameter is obtained by measuring the particle diameter (diameter) of at least 50 or more copper oxide particles by observation with a transmission electron microscope (TEM) and arithmetically averaging them. In the observation diagram, when the shape of the copper oxide particles is not a perfect circle, the major axis is measured as the diameter.
  • the content (W A ) of the copper oxide particles (A) in the composition of the present invention is not particularly limited as long as W A : W B is within the range described later, but is 5.0 to It is preferable that it is 60.0 mass%. Among these, from the reason that the conductivity of the obtained conductive film is more excellent, it is preferably 10.0 to 40.0% by mass, and preferably 15.0 to 35.0% by mass with respect to the total amount of the composition. More preferred.
  • the copper particles (B) contained in the composition of the present invention are not particularly limited as long as they are particulate copper having an average particle diameter of 100 to 3000 nm.
  • the definition of the particle shape is the same as that of the copper oxide particle (A).
  • the average particle diameter of the copper particles (B) is not particularly limited as long as it is in the range of 100 to 3000 nm, but is preferably 150 to 2000 nm because the conductivity of the obtained conductive film is more excellent. Especially, it is preferable that it is 200 nm or more and less than 500 nm because the toughness of the electrically conductive film obtained is more excellent.
  • the measuring method of an average particle diameter is the same as a copper oxide particle (A).
  • the content (W B ) of the copper particles (B) in the composition of the present invention is not particularly limited as long as W A : W B is within the range described below, but is 5.0 to 60 with respect to the total amount of the composition. It is preferably 0.0% by mass. Among these, from the reason that the conductivity of the obtained conductive film is more excellent, it is preferably 15.0 to 50.0% by mass, and preferably 20.0 to 43.0% by mass with respect to the total amount of the composition. Is more preferable.
  • the content of the copper oxide particles (A) (W A) and the content of the copper particles (B) (W B) and the mass ratio of (W A: W B) is 3: 1 to 1: 3.
  • the conductivity of the obtained conductive film is more excellent, it is preferably 2.5: 1 to 1: 3, more preferably 1: 1 to 1: 2.5. If W A : W B is out of the range of 3: 1 to 1: 3, the conductivity and toughness of the resulting conductive film will be insufficient.
  • the saccharide (C) contained in the composition of the present invention is not particularly limited.
  • the saccharide (C) include monosaccharides such as glucose, galactose, mannose, fructose, ribose and xylose; disaccharides such as lactose, sucrose, cellobiose, trehalose and maltose; trisaccharides such as raffinose and melezitose; oligosaccharides; And polysaccharides such as cellulose and starch; sugar alcohols such as xylitol, sorbitol, mannitol, and maltitol; Of these, monosaccharides or sugar alcohols (particularly sugar alcohols obtained by reducing the carbonyl group of monosaccharides) are preferred because the resulting conductive film has higher conductivity.
  • a monosaccharide from the reason for which the electroconductivity of the electrically conductive film obtained becomes higher.
  • an aldehyde group (—CHO) or a ketone group (—CO—) contained in the monosaccharide improves the reduction reactivity of the copper oxide particles. Is more excellent in conductivity.
  • the molecular weight of the saccharide (C) is not particularly limited, but is preferably 100 to 1000 from the viewpoints of coatability and removability from the film after the reduction reaction. Further, the weight average molecular weight is preferably 100 to 10,000, and more preferably 150 to 1,000. The weight average molecular weight is a polystyrene equivalent value obtained by the GPC method (solvent: N-methylpyrrolidone).
  • the total content of the copper oxide particles (A) and the copper particles (B) (W AB) and the content of the saccharide (C) (W C) and the weight ratio of (W AB : W C ) is 20: 1 to 2: 1.
  • 20: 1 to 3: 1 is preferable because the toughness of the obtained conductive film is more excellent.
  • 18: 1 to 5: 1 is preferable because the conductivity of the obtained conductive film is more excellent. If W AB : W C is out of the range of 20: 1 to 2: 1, the conductivity and toughness of the resulting conductive film will be insufficient.
  • the content of the saccharide in the composition of the present invention (C) (W C) is, W AB:
  • W C is not particularly limited as long as the above total quantity of the composition, 1.0-30. It is preferably 0% by mass. Among these, from the reason that the toughness of the obtained conductive film is more excellent, it is preferably 2.0 to 20.0% by mass relative to the total amount of the composition. Among these, from the reason that the conductivity of the obtained conductive film is more excellent, it is preferably 4.0 to 10.0% by mass with respect to the total amount of the composition.
  • the solvent (D) contained in the composition of the present invention is a solvent containing water and / or a water-soluble solvent. Especially, it is preferable that it is a solvent containing water, and it is more preferable that it is a solvent (mixed solvent) containing water and a water-soluble solvent.
  • the water-soluble solvent is not particularly limited as long as it is a water-soluble solvent.
  • alcohols eg, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol
  • ethers eg, diethyl ether, diisobutyl
  • Organic solvents such as ether, dibutyl ether, methyl-t-butyl ether) and esters (for example, methyl formate, ethyl formate, butyl formate, methyl acetate) can be used.
  • alcohols are preferable.
  • the solvent (D) may contain a plurality of water-soluble solvents.
  • the content of the solvent (D) in the composition of the present invention is not particularly limited, but is preferably 5 to 80% by mass, more preferably 10 to 60% by mass with respect to the total amount of the composition. More preferably, it is 20 to 40% by mass.
  • the composition of the present invention may contain components other than the above components.
  • the composition of the present invention may contain a surfactant.
  • the surfactant plays a role of improving the dispersibility of the copper oxide particles (A) and / or the copper particles (B).
  • 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 viscosity of the composition of the present invention is preferably adjusted to a viscosity suitable for printing applications such as inkjet and screen printing.
  • the pressure is preferably 1 to 50 cP, and more preferably 1 to 40 cP.
  • screen printing it is preferably 1000 to 100,000 cP, and more preferably 10,000 to 80,000 cP.
  • the preparation method in particular of the composition of this invention is not restrict
  • the components are dispersed 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. Can be prepared.
  • 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 manufacturing method of the electrically conductive film of this invention is a method of manufacturing an electrically conductive film using the composition of this invention mentioned above.
  • the manufacturing method of the electrically conductive film of this invention will not be restrict
  • This step is a step of applying the above-described composition of the present invention on a substrate to form a coating film.
  • a precursor film before the heat firing treatment is obtained.
  • 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.
  • a resin base material is preferable from the viewpoint of versatility.
  • low density polyethylene resin high density polyethylene resin, ABS resin, acrylic resin, styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate), polyacetal resin, polysulfone resin, polyetherimide resin, polyether ketone Resin base materials such as resin and cellulose derivatives; uncoated printing paper, fine coated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), unbleached wrapping paper ( Paper substrates such as double kraft paper for heavy bags, double kraft paper), bleached wrapping paper (bleached kraft paper, pure white roll paper), coated balls, chip balls, corrugated cardboard; soda glass, borosilicate glass, silica glass, Glass substrates such as quartz glass; silicon-based semiconductor substrates such as amorphous silicon and polysilicon; Compound semiconductor substrates such as dS, CdTe, GaAs; metal substrates such as copper plate, iron plate, aluminum plate; alumina, sapphire, zirconia
  • the method for applying the composition of the present invention on a substrate to form a coating film is not particularly limited, and a known method can be adopted.
  • Application methods include, for example, a double roll coater, slit coater, air knife coater, wire bar coater, slide hopper, spray coater, blade coater, doctor coater, squeeze coater, reverse roll coater, transfer roll coater, extrusion roll coater, curtain Examples include a coater, dip coater, die coater, gravure roll coating method, screen printing method, dip coating method, spray coating method, spin coating method, and ink jet method.
  • the screen printing method or the inkjet method is preferable, and the screen printing method is more preferable.
  • 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 of the coating film is preferably 0.01 to 5000 ⁇ m, 0.1 to 1000 ⁇ m is more preferable.
  • the composition of this invention on a base material
  • the removal of the remaining solvent is preferable because the generation of minute cracks and voids due to the vaporization and expansion of the solvent can be suppressed in the reduction step described later.
  • a conventionally known method can be used as a method for the drying treatment.
  • the temperature of the drying treatment is not particularly limited, but is preferably 80 to 200 ° C.
  • the time for the drying treatment is not particularly limited, but is preferably 1 to 30 minutes.
  • This step is a step of forming a conductive film containing copper by subjecting the coating film formed in the coating film forming process to heat baking treatment to reduce the copper oxide particles (A). By the heating and baking treatment, the copper oxide particles in the coating film and the copper oxide on the surface of the copper particles are reduced, and the copper particles are fused by the reduced copper oxide particles.
  • the conditions for the heat-firing treatment are not particularly limited, but the temperature is preferably 80 to 500 ° C., more preferably 100 to 400.
  • the temperature rising rate is preferably 100 to 1000 ° C./min.
  • the heating time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes.
  • the method of heat-firing treatment is not particularly limited, and a method using a known heat-sintering treatment device such as a sintering device (particularly, RTA (rapid thermal annealing) sintering device), an oven, a hot plate or the like is adopted. Can do.
  • the atmosphere for carrying out the heating and baking treatment is not particularly limited, and examples thereof include an air atmosphere, an inert atmosphere, and a reducing atmosphere.
  • the inert atmosphere is, for example, an atmosphere filled with an inert gas such as argon, helium, neon, or nitrogen.
  • the reducing atmosphere is a reduction of hydrogen, carbon monoxide, formic acid, alcohol, or the like. It refers to the atmosphere in which sex gas exists. Of these, a nitrogen gas atmosphere is preferable.
  • the electrically conductive film of this invention is an electrically conductive film manufactured using the composition of this invention mentioned above. Especially, it is preferable that it is an electrically conductive film manufactured with the manufacturing method provided with the coating-film formation process mentioned above and a reduction
  • the film thickness of the conductive film is not particularly limited, and an optimum film thickness is appropriately adjusted according to the intended use. Of these, 0.01 to 1000 ⁇ m is preferable and 0.1 to 100 ⁇ m is more preferable from the viewpoint of printed wiring board 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 volume resistivity of the conductive film is preferably less than 100 ⁇ ⁇ cm from the viewpoint of conductive characteristics. The volume resistivity can be calculated by measuring the surface resistance value of the conductive film by the four-probe method and then multiplying the obtained surface resistance value by the film thickness.
  • the conductive film may be provided on the entire surface of the substrate 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 conductive film forming composition is applied to a substrate in a pattern, and the heating and baking treatment is performed, or the conductive film provided on the entire surface of the substrate is patterned.
  • a method of etching 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 epoxy resin, aramid resin, crystalline polyolefin resin, amorphous polyolefin resin, fluorine-containing resin (polytetrafluoroethylene, perfluorinated polyimide, perfluorinated amorphous resin, etc.) , 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.
  • Example 1 Copper oxide particles (Ci Kasei Co., Ltd., NanoTek CuO, copper oxide (II) particles (CuO particles)) (45 parts by mass), glucose (molecular weight: 180) (7.7 parts by mass), and water (20 parts by mass) ) And ethanol (50 parts by mass) were mixed and treated with an auto-revolution mixer (manufactured by THINKY, Awatori Nertaro ARE-310) for 5 minutes to obtain a copper oxide ink composition. The average particle diameter of the copper oxide particles was 110 nm.
  • the molecular weights of the saccharides (fructose, sorbitol and maltose) used in Examples 6 to 8 are as follows.
  • Example 2 Copper particles (Mitsui Metals Mining Co., Ltd., wet copper powder 1020Y, average particle diameter: 360 nm)
  • Example 3 Copper particles (Mitsui Metals Mining Co., Ltd., wet copper powder 1030Y, average particle size: 490 nm)
  • Example 4 Copper particles (Mitsui Metals Mining Co., Ltd., wet copper powder 1100Y, average particle size: 1000 nm)
  • Example 5 Copper particles (Mitsui Metals Mining Co., Ltd., wet copper powder 1200YP, average particle diameter: 3000 nm)
  • a copper oxide ink composition was obtained according to the same procedure as in Example 1 except that polyethylene glycol (8.5 parts by mass) was added without adding glucose.
  • the average particle diameter of the copper oxide particles was 110 nm.
  • 70 parts by mass of copper particles (Mitsui Metal Mining Co., Ltd., wet copper powder 1200 YP, average particle size: 3000 nm) was added, and a revolving mixer (made by THINKY Co., Ltd., Aritori Kentaro ARE- 310) for 5 minutes to obtain a composition for forming a conductive film.
  • Copper oxide particles (Nabond, Cu 2 O nanopowder, copper oxide (I) particles (Cu 2 O particles)) (45 parts by mass), diethylene glycol (70.0 parts by mass), polyethylene glycol monoethyl ether ( 20.0 parts by mass), and a copper oxide ink composition was obtained by treating for 5 minutes with a rotating and rotating mixer (manufactured by THINKY, manufactured by Awatori Nertaro ARE-310). The average particle diameter of the copper oxide particles was 80 nm.
  • A Volume resistivity is less than 10 ⁇ ⁇ cm
  • B Volume resistivity is 10 ⁇ ⁇ cm or more and less than 50 ⁇ ⁇ cm •
  • C Volume resistivity is 50 ⁇ ⁇ cm or more and less than 100 ⁇ ⁇ cm •
  • D Volume resistivity is 100 ⁇ ⁇ cm or more and less than 1000 ⁇ ⁇ cm”
  • E Volume resistivity is 1000 ⁇ ⁇ cm or more
  • a to C in practice, more preferably A or B, and even more preferably A.
  • A increase rate is less than 10.0% of the volume resistivity due to bending test (e.g., folding volume resistivity before the test is 2.1 ⁇ 10 -5 ⁇ ⁇ cm, the volume resistivity after bending test 2.3 ⁇ 10 -5 ⁇ ⁇ cm)
  • B The increase rate of the volume resistance value by the bending test is 10.0% or more and less than 50% (for example, the volume resistivity before the bending test is 2.1 ⁇ 10 -5 ⁇ ⁇ cm, the volume after the bending test) (When the resistivity is 3.0 ⁇ 10 -5 ⁇ ⁇ cm)
  • C the increase rate of the volume resistivity value by the bending test is 50% or more and less than 100% (for example, the volume resistivity before the bending test is 2.1 ⁇ 10 ⁇ 5 ⁇ ⁇ cm, the volume resistivity after the bending test) Is 4.1 ⁇ 10 -5
  • PEG, DEG and PEGEE represent the following compounds, respectively.
  • ⁇ PEG Polyethylene glycol
  • DEG Diethylene glycol
  • PEGEE Polyethylene glycol monoethyl ether
  • the conductive films obtained from the compositions of the examples of the present application all exhibited excellent conductivity and toughness. From the comparison with Examples 1 to 5, the conductive films obtained from the compositions of Examples 1 to 4 in which the average particle diameter of the copper particles was 2000 nm or less showed better conductivity. Especially, the electrically conductive film obtained from the composition of Example 2 and 3 whose average particle diameter of a copper particle is less than 500 nm showed more superior toughness. From the comparison between Examples 1 and 6 to 8, the conductive films obtained from the compositions of Examples 1, 6 and 7 in which the saccharide was a monosaccharide or a sugar alcohol showed better toughness.
  • the conductive films obtained from the compositions of Examples 1 and 6 in which the saccharide was a monosaccharide showed more excellent conductivity.
  • the conductive films obtained from the compositions of Examples 1, 9-11, 13 and 14 in which W A : W B is 2.5: 1 to 1: 3 are: Excellent conductivity was shown.
  • the conductive films obtained from the compositions of Examples 1, 10, 11 and 14 in which W A : W B was 1: 1 to 1: 2.5 showed further excellent conductivity.
  • the conductive films obtained from the compositions of Examples 1 and 15 to 18 where W AB : W C is 20: 1 to 3: 1 show better toughness. It was.
  • the conductive films obtained from the compositions of Examples 1, 16 and 17 in which W AB : W C is 18: 1 to 5: 1 showed better conductivity.
  • the conductive films obtained from the compositions of Comparative Example 5 containing no copper oxide particles and Comparative Example 6 containing no copper particles had insufficient conductivity and toughness.
  • the conductive film obtained from the composition of Comparative Example 7 containing no saccharide had insufficient toughness.
  • Comparative Examples 1 and 2 which contain saccharides but have W AB : W C outside the range of 20: 1 to 2: 1, were insufficient in conductivity and toughness.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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Abstract

La présente invention aborde le problème de fourniture : d'une composition de formation d'un film électriquement conducteur, qui permet la formation d'un film électriquement conducteur ayant une conductivité électrique et une rigidité excellentes; un procédé de production d'un film électriquement conducteur utilisant la composition de formation d'un film électriquement conducteur ; et un film électriquement conducteur produit grâce au procédé de production. La composition de formation d'un film électriquement conducteur selon la présente invention contient au moins des particules d'oxyde de cuivre (A) ayant un diamètre moyen de particules de 10 à 500 nm, des particules de cuivre (B) ayant un diamètre moyen de particules de 100 à 3 000 nm, un sucre (C), et un solvant (D) comprenant de l'eau et/ou un solvant soluble dans l'eau, le rapport (WA:WB) de la teneur (WA) des particules d'oxyde de cuivre (A) à la teneur (WB) des particules de cuivre (B) est de 3:1 à 1:3 en masse, et le rapport (WAB:WC) de la teneur totale (WAB) des particules d'oxyde de cuivre (A) et des particules de cuivre (B) à la teneur (WC) du sucre (C) est de 20:1 à 2:1 en masse.
PCT/JP2014/065346 2013-07-10 2014-06-10 Composition de formation de film électriquement conducteur, procédé de production de film électriquement conducteur, et film électriquement conducteur WO2015005046A1 (fr)

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JP2013144810A JP2015018674A (ja) 2013-07-10 2013-07-10 導電膜形成用組成物、導電膜の製造方法、および、導電膜
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JP7104687B2 (ja) 2017-03-16 2022-07-21 旭化成株式会社 分散体並びにこれを用いた導電性パターン付構造体の製造方法及び導電性パターン付構造体
US11328835B2 (en) 2017-03-16 2022-05-10 Asahi Kasei Kabushiki Kaisha Dispersing element, method for manufacturing structure with conductive pattern using the same, and structure with conductive pattern
JP6944413B2 (ja) * 2018-06-26 2021-10-06 富士フイルム株式会社 導電膜の製造方法および導電膜
JP7172224B2 (ja) * 2018-07-19 2022-11-16 昭和電工マテリアルズ株式会社 導体形成用組成物、及び、導体層を有する物品の製造方法

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JPH01282178A (ja) * 1988-05-07 1989-11-14 Fujitsu Ltd 銅ペースト組成物およびガラスセラミック基板への導電パターン形成方法
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WO2015115235A1 (fr) * 2014-01-30 2015-08-06 富士フイルム株式会社 Composition d'encre conductrice pour jet d'encre

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