WO2015107996A1 - 複合導電性粒子、それを含む導電性樹脂組成物および導電性塗布物 - Google Patents
複合導電性粒子、それを含む導電性樹脂組成物および導電性塗布物 Download PDFInfo
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- WO2015107996A1 WO2015107996A1 PCT/JP2015/050521 JP2015050521W WO2015107996A1 WO 2015107996 A1 WO2015107996 A1 WO 2015107996A1 JP 2015050521 W JP2015050521 W JP 2015050521W WO 2015107996 A1 WO2015107996 A1 WO 2015107996A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- 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
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Definitions
- the present invention relates to composite conductive particles, a conductive resin composition containing the same, and a conductive coating.
- conductive resin compositions such as conductive pastes, conductive paints, and conductive adhesives have been used in various applications such as electronic parts and electronic circuits.
- Known conductive particles used in such a conductive resin composition include spherical or flaky silver (Ag) particles, copper (Cu) particles, and the like.
- Ag has very good conductivity, there is a problem that it is expensive, and Cu is easily oxidized, and its corrosion resistance is low, so that the conductivity cannot be maintained for a long time. is there.
- JP 2008-11175 A Patent Document 1
- JP 2004-52044 A Patent Document 2
- JP 2006-161081 A Patent Document 3
- the conductive particles are characterized by excellent conductivity, corrosion resistance, moisture resistance, and the like.
- Cu has a large specific gravity, when Cu particles are used as the core particles, the conductive particles tend to settle in the conductive resin composition, and the fundamental problem that the operability (ease of handling) is low. There is.
- conductive particles in which the surface of silica particles having a low specific gravity is coated with Ag and conductive particles in which the surface of a resin having a low specific gravity is coated with Ag have been developed.
- JP 2001-23435 (Patent Document 4), JP 61-257479 A (Patent Document 5) and JP 62-297471 (Patent Document 6) disclose reducing silicon.
- a technique for precipitating a metal particle on the surface of a silica particle by using an electroless plating method after previously treating the surface of the silica particle with a polymer polymer compound or using a silane coupling agent is disclosed. .
- Patent Document 7 conductive particles in which the surface of a resin is coated with a conductive film made of a metal, which is 70 to 90% of the surface area of the conductive film. Have disclosed composite conductive particles forming raised protrusions.
- the present invention has been made in view of the current situation as described above, and its object is to provide composite conductive particles having high conductivity and high filling property, a conductive resin composition containing the same, and conductive It is to provide an adhesive coating.
- the composite conductive particle of the present invention includes a first conductive particle having a particle size of 0.1 ⁇ m or more and 50 ⁇ m or less, and a second conductive particle having a particle size of 50 nm or more and 1000 nm or less attached to the surface of the first conductive particle.
- the first conductive particles include first particles and a first metal film that covers the surface of the first particles, and the second conductive particles include the second particles and the second particles.
- a second metal film covering the surface of the particles, wherein the particle diameter of the first conductive particles is larger than the particle diameter of the second conductive particles, and the adhesion rate of the second conductive particles to the first conductive particles Is 2% or more and 40% or less.
- the first particles and the second particles are each made of silica.
- the first metal film and the second metal film are made of at least one selected from the group consisting of silver, gold, copper, nickel, platinum, tin, and alloys thereof.
- the composite conductive particle preferably includes a protective layer containing an organic acid.
- the present invention also relates to a conductive resin composition containing the composite conductive particles as a conductive material, and a conductive coating material having a coating film formed from the conductive resin composition on a substrate.
- the composite conductive particles of the present invention have high conductivity and high filling properties. Moreover, the conductive resin composition and conductive coating material containing the composite conductive particles can have high conductivity.
- composite conductive particle 1 adheres to first conductive particle 10 having a particle diameter d 1 of 0.1 ⁇ m or more and 50 ⁇ m or less, and to the surface of first conductive particle 10.
- Second conductive particles 20 having a particle diameter d 2 of 50 nm or more and 1000 nm or less.
- the first conductive particle 10 includes a first particle 11 and a first metal coating 12 that covers the surface of the first particle 11.
- the second conductive particle 20 includes a second particle 21 and a second particle 21. And a second metal film 22 covering the surface of the film.
- the particle diameter d 1 of the first conductive particles 10 are larger than the particle diameter d 2 of the second conductive particles 20, deposition rate with respect to the first conductive particles 10 of the second conductive particles 20 is more than 2% 40% or less.
- the electroconductive particle of this invention may contain the unavoidable impurity, and may contain the other arbitrary components, as long as the effect of this invention is exhibited.
- attachment means a state where they are physically connected to each other, and is different from a state where they are simply in contact with each other. Further, this state can withstand a physical impact (for example, stirring work, coating work, etc.) applied to the conductive particles at least when the conductive particles are used.
- a physical impact for example, stirring work, coating work, etc.
- the adhesion rate of the composite conductive particles 1 (the adhesion rate of the second conductive particles 20 to the first conductive particles 10) can be calculated by the following method. That is, an electronic image of the composite conductive particle 1 is obtained using a scanning electron microscope (SEM). In the electronic image, the one surface of the particles (first conductive particles 10) having a particle diameter d 1, the particle diameter d 2 (however, d 1> d 2) a plurality of particles having a (second conductive particles 20 ) Is a composite conductive particle 1.
- SEM scanning electron microscope
- FIG. 2 is a view showing an SEM photograph of the composite conductive particles.
- the particles having the largest particle size are the first conductive particles 10
- the plurality of particles having a small particle size attached to the surface are the second conductive particles 20. That is, FIG. 2 is an SEM photograph showing one composite conductive particle 1 in the observation field.
- whether the particles are “attached” or “aggregated” can be distinguished by the relationship between the particle state and the particle diameter. For example, when a large lump formed by adhering a large number of particles (regardless of their particle size) is observed, each particle constituting this lump is distinguished as “aggregated” can do. On the other hand, as described above, a plurality of particles having the particle diameter d 2 (where d 1 > d 2 ) overlap or are connected to the surface of one particle having the particle diameter d 1. When observed, it can be distinguished into “attached state”. In addition, there are cases where particles are three-dimensionally overlapped in an electronic image. Such a state cannot be observed with an electronic image on the back surface or front surface of particles overlapping each other. The image is excluded from the observation target.
- the region occupied by the second conductive particles 20 attached to the surface of the first conductive particles 10 in the composite conductive particles 1 is the region occupied by the first conductive particles 10. It tends to show higher brightness.
- the area occupied by the first conductive particles 10 (area A in FIG. 3) in the area occupied by one composite conductive particle 1 )
- Area S1 and the area S2 of the region occupied by the second conductive particles 20 (region B in FIG. 3) can be calculated.
- the area B is all areas hatched with diagonal lines.
- the adhesion rate is computable by applying each numerical value of this area S1 and S2 to following formula (1).
- the adhesion rate of the first conductive particles 10 by the second conductive particles 20 is 2% or more and 40% or less.
- the composite conductive particle 1 can achieve both high conductivity and high filling property.
- the adhesion rate is less than 2%, the conductivity is insufficient, and when the adhesion rate exceeds 40%, the filling property is insufficient.
- the coverage is more preferably 4% or more and 35% or less.
- the shapes of the first conductive particles 10 and the second conductive particles 20 are not particularly limited, and are spherical, granular, disc-like, columnar, cubic, rectangular parallelepiped, plate-like, needle-like, fibrous, and filler-like. Each shape can have a dendritic shape.
- each shape of the first particle 11 and the second particle 21 is inherited by each shape of the first conductive particle 10 and the second conductive particle 20.
- the spherical shape does not mean a mathematical spherical shape, but refers to a spherical shape that can be judged as a spherical shape at first glance.
- the first conductive particles 10 have a particle diameter d 1 of 0.1 ⁇ m or more and 50 ⁇ m or less
- the second conductive particles 20 have a particle diameter d 2 of 50 nm or more and 1000 nm or less
- the diameter d 1 is larger than the particle diameter d 2
- each particle diameter of the 1st electroconductive particle 10 and the 2nd electroconductive particle 20 can be measured by analyzing a SEM photograph. Since each of the first conductive particles 10 and the second conductive particles 20 has such a particle diameter, the composite conductive particles 1 can have high filling properties while having high conductivity.
- the particle diameter d 1 is more preferably from 1 ⁇ m to 20 ⁇ m, further preferably from 1 ⁇ m to 5 ⁇ m, and the particle diameter d 2 is more preferably from 100 nm to 950 nm, further preferably from 100 nm to 700 nm.
- the particle diameter d 1 is an average value of the particle diameters of any 50 or more first conductive particles 10 observed in the SEM photograph.
- the particle diameter d 2 is the SEM photograph. This is the average value of the particle diameters of any 50 or more second conductive particles 20 observed.
- the diameters of the first conductive particle 10 and the second conductive particle 20 are defined as the particle diameter d 1 and the particle diameter d 2 , respectively. To do.
- the shape of the 1st electroconductive particle 10 or the 2nd electroconductive particle 20 has the edge
- the distance between the long sides is defined as a particle diameter d 1 and a particle diameter d 2 .
- the material of the first particles 11 constituting the core of the first conductive particles 10 and the second particles 21 constituting the core of the second conductive particles 20 is not particularly limited, and is a metal such as aluminum, copper, nickel, or tin. Various inorganic materials such as silica, glass, alumina, and ceramics, and organic materials such as resins can be used. However, the material of the first particles 11 and the second particles 21 are made of the same material. This is due to the manufacturing method described later.
- the first particles 11 and the second particles 21 are preferably made of a material having a low specific gravity.
- resin, silica, alumina, aluminum, glass, zirconia It is preferably made of any one of silicon carbide, boron nitride and diamond.
- the resin is not particularly limited.
- Polymer resins divinylbenzene-styrene copolymers, divinylbenzene-acrylate copolymers, divinylbenzene-based copolymer resins such as divinylbenzene-methacrylate copolymers, polyalkylene terephthalates, polysulfones, polyamides, polycarbonates , Melamine formaldehyde resin, phenol formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, etc. Door can be.
- the silica fused silica or nonporous material obtained by surface treatment thereof can be suitably used.
- the glass is not particularly limited and can be appropriately selected according to the purpose. However, lead-free glass is preferable from the viewpoint of reducing environmental load.
- the metal may be contained as a component which comprises glass.
- the first particles 11 and the second particles 21 are preferably made of silica. Since silica has higher wettability than a resin, a metal film can be uniformly formed on the surface of silica particles in the production method described later. Therefore, the composite conductive particle 1 having the first particles 11 and the second particles 21 made of silica can have the homogeneous first metal coating 12 and the second metal coating 22. In addition, since silica has less change due to heat shrinkage and less swelling due to a solvent than resin, by using the first particles 11 and the second particles 21 as silica particles, the composite conductive particles 1 with more stable quality can be obtained. Can be provided.
- the shapes of the first particles 11 and the second particles 21 are not particularly limited, and each shape such as a spherical shape, a granular shape, a plate shape, a needle shape, a fiber shape, a disk shape, a columnar shape, a cube shape, a rectangular parallelepiped shape, a filler shape, a dendritic shape, etc. Can have.
- grains 21 is spherical from the height of the dispersibility in the plating process liquid in the manufacturing method mentioned later. In this case, the quality of the composite conductive particle 1 can be made more uniform.
- the materials of the first metal film 12 that covers the first conductive particles 10 and the second metal film 22 that covers the second conductive particles 20 are not particularly limited, and known metals can be used. However, the material of the first metal coating 12 and the material of the second metal coating 22 are the same. This is due to the manufacturing method described later. Among these, since silver (Ag), gold (Au), copper (Cu), nickel (Ni), platinum (Pt), tin (Sn), and their alloys have particularly high conductivity, the first metal coating 12
- the second metal coating 22 is preferably made of at least one selected from the group consisting of silver, gold, copper, nickel, platinum, tin, and alloys thereof.
- each of the first metal film 12 and the second metal film 22 may be composed of one metal layer, or may be composed of a plurality of layers made of the same kind of metal or different kinds of metals.
- the first metal film and the second metal film include phosphorus (P), boron (B), carbon (C), and sulfur (S Nonmetals such as) may be included.
- the first metal coating 12 preferably covers the entire surface of the first particle 11, but is not limited thereto, and may cover a part of the surface of the first particle 11. However, it is preferable to cover at least 70% of the surface of the first particle 11 from the viewpoint of sufficiently exhibiting the effect.
- the second metal coating 22 also preferably covers the entire surface of the second particle 21, but is not limited thereto, and may cover a part of the surface of the second particle 21. However, it is preferable that at least 70% of the surface of the second particle 21 is covered from the viewpoint of sufficiently exhibiting the effect.
- the average film thickness of the first metal film 12 and the second metal film 22 is preferably 0.1 nm or more. When the thickness is less than 0.1 nm, it is difficult to coat each composite conductive particle 1, which tends to cause a decrease in conductivity.
- the film thickness is more preferably 1 nm or more.
- the film thickness is more preferably 100 nm or less. When the film thickness exceeds 100 nm, the variation in the film thickness tends to increase, and the film tends to aggregate easily. Furthermore, since it is necessary to increase the amount of metal to be used in order to increase the film thickness, the manufacturing cost tends to increase. For this reason, it is preferable to consider the trade-off between required conductivity and manufacturing cost.
- the film thicknesses of the first metal film 12 and the second metal film 22 can be evaluated by observing the cross section of the composite conductive particle 1 using an electron microscope such as SEM.
- the uniformity of the coating of the first particles 11 (second particles 21) with the first metal coating 12 (second metal coating 22), the degree of coating, and the like can also be evaluated by the same cross-sectional observation.
- the composite conductive particle 1 may include a protective layer that covers the surface (not shown).
- the protective layer can be formed of a surface treatment agent such as a fatty acid or a fatty acid salt.
- the composite conductive particles 1 are provided with a protective layer on the surface, whereby heat resistance is improved, and thus conductivity is maintained.
- the protective layer preferably covers the entire surface of the composite conductive particle 1, but is not limited thereto, and may be configured to cover a part of the composite conductive particle 1. This protective layer also functions as a dispersant or a lubricant for the composite conductive particles when the composite conductive particles are blended into the conductive resin composition.
- the surface treatment agent is not particularly limited and can be appropriately selected according to the purpose.
- examples thereof include fatty acids, fatty acid salts, surfactants, chelating agents, and organometallic compounds. Of these, fatty acids and fatty acid salts are preferable, and benzotriazoles are preferable in addition to these.
- fatty acids include propionic acid, caprylic acid, lauric acid, palmitic acid, oleic acid, acrylic acid, myristic acid, stearic acid, behenic acid, linoleic acid, arachidonic acid and the like.
- a surface treating agent may be used individually by 1 type, and may use 2 or more types together.
- grains 21 is prepared.
- the powder include powder made of inorganic particles such as metal powder, resin powder, and silica powder.
- the shape of the powder to be used is not particularly limited, and each shape such as a spherical shape, a granular shape, a plate shape, a needle shape, a fiber shape, a filler shape, and a dendritic shape can be used. In view of the high nature, it is preferably spherical.
- the 1st conductive particle 10 and the 2nd conductive particle 20 which comprise the composite conductive particle 1 manufactured also become spherical. .
- the powder is a material of the first particles 11 and second particles 21 to be used, the said powder, at least, the small particles having a particle size smaller than the particle diameter d 2 of the second conductive particles 20, larger than the small particles, and the particle size d 1 of the first conductive particles 10 (wherein, d 1> d 2) is necessary and large particles are mixed with a particle size smaller than.
- the D50 of the powder is preferably 1 ⁇ m to 50 ⁇ m
- the D10 is preferably 0.1 ⁇ m to 10 ⁇ m
- more preferably the D10 is 0.1 ⁇ m to 1 ⁇ m.
- D50 and D10 mean particle diameters of 50% and 10% cumulative degree, respectively, in the volume cumulative particle size distribution measured by the laser diffraction method.
- the powder having the particle size distribution as described above may be used as the whole powder, or the small particles and the large particles as described above are prepared separately. And you may prepare the powder which mixed these beforehand. Furthermore, in mixing, the mixing ratio may be adjusted in consideration of the coverage of the composite conductive particles 1.
- the prepared powder is put into a stirring tank of a stirring device, and this is slurried.
- the stirring device for example, the stirring device shown in FIG. 4 can be used.
- the agitation device 30 includes an agitation tank 31 and an agitation blade 32 capable of agitating the slurry and the like accommodated in the agitation tank 31.
- the stirring blade 32 includes a support shaft portion 32a and a blade portion 32b, and can be rotated at a predetermined blade peripheral speed in a direction indicated by an arrow in the drawing by a driving unit (not shown).
- a slurry made of powder is put into the stirring tank 31.
- a catalyst for covering the surfaces of the first particles 11 and the second particles 21 with the first metal film 12 and the second metal film 22 is put into the stirring tank 31.
- the first metal film 12 and the second metal film 22 can also be formed by directly contacting the surface of the first particle 11 and the second particle 21 with the plating solution without applying a catalyst.
- a metal coating is more efficiently formed by attaching a catalyst for electroless plating to each particle before the electroless plating treatment, it is preferable to input the catalyst.
- Examples of the method of attaching the catalyst include a method of treating the surfaces of the first particles 11 and the second particles 21 with a hydrochloric acid solution containing stannous chloride and then treating with a solution containing palladium chloride, palladium chloride and chloride chloride.
- a plating solution containing a metal salt, a reducing agent, and a complexing agent is put into the stirring tank 31.
- the metal salt those that can be stably dissolved in a mixed solvent including an organic solvent and an aqueous solvent are preferable. Nitrate, sulfate, nitrite, oxalate, carbonate, chloride, acetate, lactate, sulfamine Acid salts, fluorides, iodides, cyanides and the like can be used.
- the metal constituting the metal salt is a metal constituting the first metal film 12 and the second metal film 22.
- reducing agent known ones used in the electroless plating method can be used. Specifically, sugars such as glucose and saccharose, polysaccharides such as cellulose, starch and glycogen, polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin, hypophosphorous acid, formaldehyde, boron borohydride, dimethylamine borane , Trimethylamine borane, hydrazine tartaric acid, and salts thereof can be used.
- the hydrazine arsenate is preferably an alkali metal salt.
- the complexing agent known ones used in the electroless plating method can be used. Specifically, carboxylic acids such as succinic acid, oxycarboxylic acids such as citric acid and arsenic acid, glycine, ethylenediaminetetraacetic acid (EDTA), aminoacetic acid, and salts thereof such as alkali metal salts and ammonium salts Etc. can be used.
- carboxylic acids such as succinic acid
- oxycarboxylic acids such as citric acid and arsenic acid
- glycine ethylenediaminetetraacetic acid (EDTA), aminoacetic acid
- salts thereof such as alkali metal salts and ammonium salts Etc.
- the pH of the plating treatment solution is preferably adjusted as appropriate depending on the type of metal constituting the metal salt.
- the pH can be adjusted to alkaline (pH 8-12), and by adding sulfuric acid, nitric acid, citric acid, etc.
- the pH can be neutral (pH 6 to 8) by combining these.
- the temperature of the plating treatment solution is preferably adjusted to 1 to 99 ° C. In this case, the plating reaction can proceed efficiently.
- the electroless plating process is performed by rotating the stirring blade 32 and stirring the plating solution.
- the peripheral speed of the stirring blade 32 is controlled to 1.5 m / sec or more and 10 m / sec or less.
- the relationship (D1: D2) between the inner diameter D1 of the stirring tank 31 and the outer diameter D2 of the stirring blade 32 is preferably 7: 3 to 5: 5, and 7: 3 to 6: 4 is more preferable.
- the control of the blade peripheral speed can be reflected uniformly.
- the relationship (H1: H2) between the height H1 of the plating solution in the stirring tank 31 and the height H2 of the stirring blade 32 is 9.9: 0.1 to 7: 3. It is preferably 9.9: 0.1 to 9: 1.
- the height H1 corresponds to the distance between the upper surface of the bottom of the stirring tank 31 and the surface of the plating solution
- the height H2 corresponds to the distance between the upper surface of the bottom and the lower surface of the blade 32b.
- a baffle (baffle) may be installed on the inner wall of the stirring tank 31 in order to improve the dispersibility in the vertical direction in the stirring tank 31.
- the composite electroconductive particle 1 is produced in the plating solution by the electroless plating process. Therefore, the slurry of the composite conductive particles 1 can be obtained by solid-liquid separation of the stirred slurry (plating solution), and the composite conductive particles 1 can be obtained by drying the slurry.
- the forming method is not particularly limited.
- the composite conductive particles 1 are taken out from the processing liquid after the electroless plating process by solid-liquid separation or the like, and this is used as the protective layer. It is possible to adopt a method of charging into a solution containing a fatty acid or an organic acid as the material. By this treatment, composite conductive particles 1 having a protective layer can be produced.
- the composite conductive particle 1 can be efficiently manufactured by performing an electroless plating process under specific conditions.
- conductive particles in which the surface of each particle is coated with a metal are produced by the simple treatment as described above, and among the conductive particles, “large-diameter conductive particles having a particle diameter d 1 ”.
- the second conductive particles 20 that are a plurality of “small-diameter conductive particles” having a particle diameter d 2 (where d 1 > d 2 ) can adhere to the surface of the first conductive particles 10. .
- a metal salt-derived metal is deposited on the surface of various large and small particles.
- conductive particles having various particle diameters are produced.
- the blade peripheral speed at this time is less than 1.5 m / sec, the dispersibility of the slurry is lowered, and therefore all the conductive materials including “large-diameter conductive particles” and “small-diameter conductive particles” are included. Particles coagulate. In this case, not only “small-diameter conductive particles” are attached to one “large-diameter conductive particle”, but also other “large-diameter conductive particles” are attached.
- the electroconductive particle 1 cannot be manufactured. This state corresponds to the “aggregated state” described above.
- the dispersibility of the slurry becomes high, so that the “large-diameter conductive particles” and the “small-diameter conductive particles” are each coated with a metal after being coated with each other. It becomes difficult to contact. For this reason, the “small-diameter conductive particles” cannot be attached to the surface of the “large-diameter conductive particles”, and the respective conductive particles remain dispersed. In general, it is desirable that each particle is dispersed in performing the plating process.
- the blade peripheral speed is 1.5 m / sec or more and 10 m / sec or less
- the dispersibility of the slurry does not cause aggregation as described above, and “large-diameter conductive particles” and “small-diameter conductive”. It becomes a state suitable for contacting after each of the “particles” is coated. For this reason, a plurality of “small-diameter conductive particles” can adhere to one “large-diameter conductive particle”, and as a result, the composite conductive particle 1 is manufactured.
- the composite conductive particle 1 according to the present embodiment can have high conductivity and high filling properties.
- the reason why the composite conductive particles 1 can have both the high conductivity and the high filling property is considered as follows.
- the conventional conductive particles have a configuration in which a metal film is formed on the surface of one core particle.
- the composite conductive particle 1 has a configuration in which a plurality of second conductive particles 20 having a relatively small particle size are attached to the surface of the first conductive particle 10 having a relatively large particle size.
- each of the first conductive particle 10 and the second conductive particle 20 has a configuration of being individually coated with a metal coating as shown in FIG. That is, the first particles 11 and the second particles 21 are not in direct contact with each other.
- the structure of the composite conductive particle 1 is different from, for example, a configuration in which the surfaces of a plurality of particles that are in direct contact with each other are integrally covered with metal. Since the composite conductive particles 1 are attached to each other in a state where the first particles 11 and the second particles 21 are respectively coated as compared with a structure in which the composite conductive particles 1 are integrally covered with metal, Conduction is also possible at the contact point between the particle 10 and the second conductive particle 20, and thus higher conductivity can be achieved.
- the coverage of the first conductive particles 10 by the second conductive particles 20 is too high, or the particle diameter of the second conductive particles 20 is too large, the structure of the composite conductive particles 1 becomes bulky. It is considered that the filling property is lowered.
- the coverage is 2% or more and 40% or less, and the particle diameter d 1 of the first conductive particle 10 and the particle diameter of the second conductive particle 20.
- the conductive resin composition according to the present embodiment includes the above-described composite conductive particle 1 as a conductive material.
- the composite conductive particle 1 has high conductivity and high filling property as described above, and the conductive resin composition containing this as a conductive material takes over the effect of the composite conductive particle 1 described above. Can do. That is, according to the conductive composition of the present invention, the composite conductive particles 1 having high conductivity can be contained, and the composite conductive particles 1 can be filled at a high density in the conductive resin composition. Therefore, a highly conductive conductive resin composition can be provided.
- the conductive resin composition is obtained by dispersing the composite conductive particles 1 in a resin.
- a conductive paste, a conductive paint, a conductive adhesive, a conductive ink, a conductive film examples thereof include conductive moldings and conductive coating films.
- Such a conductive resin composition can be produced, for example, by kneading the composite conductive particles 1 into a resin or dispersing the composite conductive particles 1 in a resin solution.
- thermosetting acrylic resin / melamine resin thermosetting acrylic resin / cellulose acetate butyrate (CAB) / melamine resin.
- thermosetting polyester (alkyd) resin / melamine resin thermosetting polyester (alkyd) / CAB / melamine resin
- isocyanate curable urethane resin / room temperature curable acrylic resin water diluted acrylic emulsion / melamine resin, etc.
- content of the electroconductive particle in an electroconductive resin composition changes with uses, it is not specifically limited, For example, it is preferable to set it as 10 to 100 mass parts with respect to 100 mass parts of resin. When the amount is less than 10 parts by mass, the conductivity of the conductive resin composition may be insufficient. When the amount exceeds 100 parts by mass, the amount of the conductive particles in the conductive resin composition is too large. May decrease.
- the conductive resin composition may contain any component other than the resin and the composite conductive particles 1. Examples of the optional component include glass frit, metal alkoxide, viscosity adjusting agent, surface adjusting agent and the like.
- the conductive coating according to the present embodiment is a coating having a coating formed on the substrate with the conductive resin composition. Therefore, this conductive coating material has high conductivity.
- the conductive coating material include electrodes, wirings, circuits, conductive bonding structures, and conductive adhesive tapes.
- the shape and thickness of the coating film are not particularly limited, and a desired thickness can be adopted depending on the application.
- the materials thereof are not particularly limited, such as organic materials such as metals and plastics, inorganic materials such as ceramics and glass, paper and wood.
- substrate can be employ
- Example 1 The conductive powder (composite conductive particles) according to Example 1 was produced as follows. First, silica powder (trade name: “Admafine SO-C6”, manufactured by Admatechs Co., Ltd.) was prepared as a material for the first particles and the second particles. The characteristics of this powder were as follows. Specific surface area: 35922 cm 2 / cm 3 D10: 0.69 ⁇ m D50: 1.83 ⁇ m.
- a stirrer having a configuration as shown in FIG. 4 was prepared.
- the maximum capacity of the stirring tank is 2.0 L
- the relationship (D1: D2) between the inner diameter D1 of the stirring tank and the outer diameter D2 of the stirring blade is within the range of 7: 3 to 6: 4 Met.
- the relationship between the height H1 of the plating solution in the stirring tank and the height H2 of the stirring blade (H1: H2) is within the range of 9.9: 0.1 to 9: 1. It was.
- Aqueous solution 1 An aqueous solution in which 6.75 g of silver nitrate and 30 mL of 25% ammonia water are dissolved in 300 mL of ion-exchanged water
- Aqueous solution 2 An aqueous solution in which 2.7 g of sodium hydroxide is dissolved in 300 mL of ion-exchanged water
- Aqueous solution 3 40.5 g of glucose An aqueous solution dissolved in 300 mL of ion exchange water.
- the treatment liquid after the above plating treatment was subjected to solid-liquid separation, and the obtained solid component B was washed with ion exchange water.
- the composite electroconductive particle which concerns on this invention which has the structure shown by FIG. 1 will be contained.
- the obtained solid component B after washing is added to an oleic acid-containing alcohol solution charged into another stirring tank and stirred for 10 minutes, so that the surface of the composite conductive particles is coated with oleic acid. A protective layer was formed.
- the oleic acid-containing alcohol solution a solution in which 2 g of oleic acid was dissolved in 100 mL of isopropyl alcohol was used.
- the obtained slurry was subjected to solid-liquid separation, and the obtained solid component C was washed with ion-exchanged water.
- the solid component obtained here contains composite conductive particles having a protective layer. Then, the obtained solid component C after washing was dried at 110 ° C. in a vacuum environment to obtain a conductive powder according to Example 1.
- the conductive powder had a brown color tone.
- Example 2 The conductive powder (composite conductive particles) according to Example 2 was produced as follows. First, silica powder (trade name: “Admafine SO-C6”, manufactured by Admatechs Co., Ltd.) was prepared as a material for the first particles and the second particles.
- silica powder trade name: “Admafine SO-C6”, manufactured by Admatechs Co., Ltd.
- Aqueous solution 1 An aqueous solution in which 1.75 g of silver nitrate and 8 mL of 25% aqueous ammonia are dissolved in 50 mL of ion-exchanged water
- Aqueous solution 2 An aqueous solution in which 0.7 g of sodium hydroxide is dissolved in 50 mL of ion-exchanged water
- Aqueous solution 3 10.5 g of glucose An aqueous solution dissolved in 50 mL of ion exchange water.
- the treatment liquid after the above plating treatment was subjected to solid-liquid separation, and the obtained solid component B was washed with ion exchange water.
- the composite electroconductive particle which concerns on this invention which has the structure shown by FIG. 1 will be contained.
- the obtained solid component B after washing is added to an oleic acid-containing alcohol solution charged into another stirring tank and stirred for 10 minutes, so that the surface of the composite conductive particles is coated with oleic acid. A protective layer was formed.
- the oleic acid-containing alcohol solution a solution in which 1.5 g of oleic acid was dissolved in 0.3 L of isopropyl alcohol was used.
- the obtained slurry was subjected to solid-liquid separation, and the obtained solid component C was washed with ion-exchanged water.
- the solid component C obtained here contains composite conductive particles having a protective layer.
- the obtained solid component C after washing was dried at 110 ° C. in a vacuum environment to obtain a conductive powder according to Example 2.
- the color tone of the conductive powder was black brown.
- Example 3 A conductive powder (composite conductive particles) according to Example 3 was produced as follows. First, silica powder (trade name: “Admafine SO-C6”, manufactured by Admatechs Co., Ltd.) was prepared as a material for the first particles and the second particles.
- silica powder trade name: “Admafine SO-C6”, manufactured by Admatechs Co., Ltd.
- Aqueous solution 1 An aqueous solution in which 3.9 g of silver nitrate and 18 mL of 25% ammonia water are dissolved in 110 mL of ion-exchanged water
- Aqueous solution 2 An aqueous solution in which 1.5 g of sodium hydroxide is dissolved in 110 mL of ion-exchanged water
- Aqueous solution 3 23.6 g of glucose An aqueous solution dissolved in 110 mL of ion exchange water.
- the treatment liquid after the above plating treatment was subjected to solid-liquid separation, and the obtained solid component B was washed with ion exchange water.
- the composite conductive particles according to the present invention having the configuration shown in FIG. 1 are included.
- the obtained solid component B after washing is added to an oleic acid-containing alcohol solution charged into another stirring tank and stirred for 10 minutes, so that the surface of the composite conductive particles is coated with oleic acid. A protective layer was formed.
- the oleic acid-containing alcohol solution a solution in which 1.5 g of oleic acid was dissolved in 0.3 L of isopropyl alcohol was used.
- the obtained slurry was subjected to solid-liquid separation, and the obtained solid component C was washed with ion-exchanged water.
- the solid component C obtained here contains composite conductive particles having a protective layer. Then, the obtained solid component C after washing was dried at 110 ° C. in a vacuum environment to obtain a conductive powder according to Example 3.
- the conductive powder had a grayish brown color tone.
- Example 4 A conductive powder (composite conductive particles) according to Example 4 was produced as follows. First, silica powder (trade name: “Admafine SO-C6”, manufactured by Admatechs Co., Ltd.) was prepared as a material for the first particles and the second particles.
- silica powder trade name: “Admafine SO-C6”, manufactured by Admatechs Co., Ltd.
- Aqueous solution 1 An aqueous solution in which 10.5 g of silver nitrate and 47 mL of 25% ammonia water are dissolved in 300 mL of ion-exchanged water
- Aqueous solution 2 An aqueous solution in which 4.2 g of sodium hydroxide is dissolved in 300 mL of ion-exchanged water
- Aqueous solution 3 63 g of glucose is ion-exchanged An aqueous solution dissolved in 300 mL of water.
- the treatment liquid after the above plating treatment was subjected to solid-liquid separation, and the obtained solid component B was washed with ion exchange water.
- the composite conductive particles according to the present invention having the configuration shown in FIG. 1 are included.
- the obtained solid component B after washing is added to an oleic acid-containing alcohol solution charged into another stirring tank and stirred for 10 minutes, so that the surface of the composite conductive particles is coated with oleic acid. A protective layer was formed.
- the oleic acid-containing alcohol solution a solution in which 1.5 g of oleic acid was dissolved in 0.3 L of isopropyl alcohol was used.
- the obtained slurry was subjected to solid-liquid separation, and the obtained solid component C was washed with ion-exchanged water.
- the solid component C obtained here contains composite conductive particles having a protective layer. Then, the obtained solid component C after washing was dried at 110 ° C. in a vacuum environment to obtain a conductive powder according to Example 4. The color tone of the conductive powder was yellowish white.
- Example 5 A conductive powder (composite conductive particles) according to Example 5 was produced as follows. First, as a material for the first particles and the second particles, silica powder manufactured by Admatechs Inc. was prepared. The characteristics of this powder were as follows. Specific surface area: 7577 cm 2 / cm 3 D10: 8.55 ⁇ m D50: 16.24 ⁇ m.
- a stirrer having a configuration as shown in FIG. 4 was prepared.
- the maximum capacity of the stirring tank was 5.0 L
- the ratios of D1: D2 and H1: H2 were the same as those in Example 1.
- Aqueous solution 1 An aqueous solution in which 14 g of nickel sulfate is dissolved in 30 ml of ion-exchanged water
- Aqueous solution 2 An aqueous solution in which 3.1 g of sodium hypophosphite is dissolved in 30 ml of ion-exchanged water
- Aqueous solution 3 3.0 g of sodium succinate in ion-exchanged water
- the treatment liquid after the plating treatment was subjected to solid-liquid separation, and the obtained solid component C was washed with ion-exchanged water.
- the composite electroconductive particle which concerns on this invention which has the structure shown by FIG. 1 will be contained.
- the obtained solid component C after washing was dried at 110 ° C. in a vacuum environment to obtain a conductive powder according to Example 5.
- the color tone of this conductive powder was black.
- Example 1 The same method as in Example 1 was carried out except that the blade peripheral speed in the plating treatment was 20 m / sec. Thereby, the electroconductive powder which concerns on the comparative example 1 was produced. In addition, the color tone of this electroconductive powder was gray.
- Example 1 For each conductive powder of Examples 1 to 5 and Comparative Example 1, the particle diameter of each particle was obtained by analyzing each SEM photograph obtained by performing SEM observation as shown in FIGS. It was. In Example 1, composite conductive particles in which a plurality of particles having a smaller particle size (second conductive particles) are attached to the surface of one particle (first conductive particle) having a large particle size. Therefore, the particle diameters of the first conductive particles and the second conductive particles were determined. The results are shown in “Particle size ( ⁇ m)” in Table 1. Each particle diameter is an average value of the diameters of 50 particles arbitrarily selected from SEM photographs obtained by SEM observation in a plurality of fields of view.
- ⁇ Adhesion rate> For the conductive powders of Examples 1 to 5, the SEM photographs as shown in FIG. 5 were analyzed to determine the adhesion rate of the second conductive particles to the first conductive particles. In addition, regarding the calculation of the adhesion rate, the above calculation method was followed using image processing software (product name: “WinROOF”, Mitani Corporation). The results are shown in the column “attachment rate (%)” in Table 1. The adhesion rate is an average value of 50 arbitrarily selected composite conductive particles.
- ⁇ Metal coverage> For each of the conductive powders of Examples 1 to 5 and Comparative Example 1, the metal coverage was calculated. Specifically, the calculation was performed according to the following procedure. First, the weight of each conductive powder before determination of the amount of metal by an atomic absorption photometer (weight of the conductive powder before dissolution with an acid solution) was measured. Next, each sample in which each conductive powder whose weight was measured was dissolved in an acid solution was prepared.
- each of the above samples is obtained by collecting a suitable amount of conductive particles, dissolving the mixture with nitric acid and hydrofluoric acid over 30 minutes at room temperature, and diluting to a concentration suitable for measurement.
- the measurement wavelengths were 328.1 nm (silver) and 232.0 nm (nickel), and the gas conditions were air-acetylene.
- Metal coating amount (% by weight) W1 / W2 ⁇ 100 (2) (In Formula (2), W1 shows the weight of the metal which comprises a metal film, and W2 shows the weight of the electroconductive powder before melt
- each conductive powder and resin (trade name: “Nippe Acrylic Auto Clear Super”, manufactured by Nippon Paint Co., Ltd.) are kneaded so that the blending ratio (conductive powder: resin) is 60 vol%: 40 vol%. And the resin composition containing each electroconductive powder was produced.
- each resin composition was apply
- the thickness of the coating film was confirmed by measuring with a digimatic standard outer micrometer (trade name: “IP65 COOLANT PROOF Micrometer”, manufactured by Mitutoyo Corporation).
- the tap density of each conductive powder of Examples 1 to 5 and Comparative Example 1 was measured to evaluate the filling property of each conductive powder.
- the tap density can be measured by a method based on JIS Z2512: 2012.
- the tapping density was measured by using a tapping powder reduction measuring instrument (model: “TPM-1”, manufactured by Tsutsui Riken Kikai Co., Ltd.).
- TPM-1 tapping powder reduction measuring instrument
- the results are shown in “Tap Density (g / cm 3 )” in Table 2. The larger the tap density, the better the filling property.
- Example 1 When comparing Example 1 and Comparative Example 1 with reference to Table 1 and Table 2, the conductive powder of Example 1 has the conductivity of Comparative Example 1 even though the coverage of the metal film is equivalent. A coating film having a specific resistance lower than that of the powder could be formed.
- the conductive powders of Examples 1 to 5 showed higher tap density than the conductive powder of Comparative Example 1. Thereby, it was confirmed that the composite conductive powder can exhibit both characteristics of high conductivity and high filling property.
- the cross section of the conductive powder of Example 1 was observed. First, an epoxy resin and conductive powder were mixed and cured, and a sample for cross-sectional observation of the conductive powder was prepared using an ion milling device. Using a scanning electron microscope (trade name: “SU8020”, manufactured by Hitachi High-Technology Co., Ltd.), the cross section of the conductive powder in the sample was observed under the conditions of an acceleration voltage of 50 kV and a measurement magnification of 30000 times. An image (electronic image) was taken.
- FIG. 8 shows an SEM photograph of a cross section of the conductive powder of Example 1. From FIG. 8, in the conductive powder of Example 1, the surface of the silica particles as the first particles is coated with the silver coating as the first metal film in the first conductive particles, The surface of the silica particles as two particles is covered with a silver coating as a second metal coating, the first conductive particles are larger than the second conductive particles, and the second conductive property is formed on the surface of the first conductive particles. It was confirmed that the particles adhered.
- each cross section was observed by the same method as in Example 1.
- the surface of the silica particles as the first particles was the first.
- a metal film that is a metal film (a silver film in Examples 2 to 4 and a nickel-phosphorus film in Example 5) is coated, and in the second conductive particles, the surface of the silica particles that are the second particles is the second metal film.
- Is coated with a metal coating (a silver coating in Examples 2 to 4, a nickel-phosphorus coating in Example 5), and the first conductive particles are larger than the second conductive particles. It was confirmed that the second conductive particles adhered to the surface.
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Abstract
Description
また、本発明は、上記の複合導電性粒子を導電材として含む導電性樹脂組成物、および該導電性樹脂組成物により形成された塗膜を基体上に有する導電性塗布物にも係わる。
図1を参照し、本実施の形態に係る複合導電性粒子1は、0.1μm以上50μm以下の粒子径d1を有する第1導電性粒子10と、第1導電性粒子10の表面に付着する、50nm以上1000nm以下の粒子径d2を有する第2導電性粒子20とを備える。第1導電性粒子10は、第1粒子11と、第1粒子11の表面を被覆する第1金属被膜12とからなり、第2導電性粒子20は、第2粒子21と、第2粒子21の表面を被覆する第2金属被膜22とからなる。また、第1導電性粒子10の粒子径d1は、第2導電性粒子20の粒子径d2よりも大きく、第2導電性粒子20の第1導電性粒子10に対する付着率は2%以上40%以下である。なお、本発明の導電性粒子は、不可避不純物を含んでいてもよく、また、本発明の効果を発揮する限り、他の任意の成分を含んでいてもよい。
まず、付着率について説明する。複合導電性粒子1の付着率(第2導電性粒子20の第1導電性粒子10に対する付着率)は次の方法により算出することができる。すなわち、走査型電子顕微鏡(SEM;Scanning Electron Microscope)を用いて、複合導電性粒子1の電子画像を得る。電子画像において、粒子径d1を有する1つの粒子(第1導電性粒子10)の表面に、粒子径d2(ただし、d1>d2)を有する複数の粒子(第2導電性粒子20)が付着している構造を示すものが、複合導電性粒子1に該当する。
付着率(%)=S2/(S1+S2)×100・・・(1)。
図1に戻り、第1導電性粒子10および第2導電性粒子20の形状は特に制限されず、球状、粒状、円盤状、柱状、立方体、直方体、板状、針状、繊維状、フィラー状、樹枝状などの各形状を有することができる。製造方法上、第1粒子11および第2粒子21の各形状は、第1導電性粒子10および第2導電性粒子20の各形状に引き継がれる。なお、本明細書において、球状とは、数学的な球形を意図するものではなく、一見して球形と判断できる程度のものをいう。
第1導電性粒子10のコアを構成する第1粒子11、および第2導電性粒子20のコアを構成する第2粒子21の材料は特に制限されず、アルミニウム、銅、ニッケル、錫などの金属、シリカ、ガラス、アルミナ、セラミックスなどの種々の無機物、樹脂などの有機物を用いることができる。ただし、第1粒子11の材料と第2粒子21とは同じ材料からなる。これは、後述する製造方法に起因する。
第1導電性粒子10を被覆する第1金属被膜12、および第2導電性粒子20を被覆する第2金属被膜22の材料は特に制限されず、公知の金属を用いることができる。ただし、第1金属被膜12の材料と第2金属被膜22の材料とは同じである。これは、後述する製造方法に起因する。なかでも、銀(Ag)、金(Au)、銅(Cu)、ニッケル(Ni)、白金(Pt)、錫(Sn)およびこれらの合金は特に高い導電性を有するため、第1金属被膜12および第2金属被膜22は、銀、金、銅、ニッケル、白金、錫およびこれらの合金からなる群より選ばれる少なくとも1種からなることが好ましい。また、第1金属被膜12および第2金属被膜22は、各々1層の金属層で構成されてもよく、同種の金属または異種の金属からなる複数層で構成されてもよい。また、金属の導電性を大きく阻害せず、本発明の効果を奏する限り、第1金属被膜および第2金属被膜には、リン(P)、ホウ素(B)、炭素(C)および硫黄(S)等の非金属が含まれていてもよい。
複合導電性粒子1は、その表面を被覆する保護層を備えていてもよい(不図示)。当該保護層は脂肪酸または脂肪酸塩などの表面処理剤により形成することができる。複合導電性粒子1がその表面に保護層を備えることによって耐熱性が向上し、これにより導電性が維持される。なお、保護層は、複合導電性粒子1の表面の全体を被覆していることが好ましいが、これに限られず、複合導電性粒子1の一部を被覆している構成であってもよい。この保護層は、複合導電性粒子を導電性樹脂組成物に配合した際に、複合導電性粒子の分散剤や潤滑剤としての機能も果たす。
複合導電性粒子1の製造方法について説明する。まず、第1粒子11および第2粒子21の材料となる粉末を準備する。粉末としては、金属粉末、樹脂粉末、およびシリカ粉末などの無機物の粒子からなる粉末などが挙げられる。用いられる粉末の形状は特に制限されず、球状、粒状、板状、針状、繊維状、フィラー状、樹枝状などの各形状のものを用いることができるが、後述するめっき処理液中における分散性の高さから、球状であることが好ましい。なお、第1粒子11および第2粒子21の材料の形状が球状である場合、製造される複合導電性粒子1を構成する第1導電性粒子10および第2導電性粒子20もまた球状となる。
本実施の形態に係る複合導電性粒子1によれば、高い導電性と高い充填性とを有することができる。複合導電性粒子1が高い導電性と高い充填性との両特性を有することのできる理由は次のように考えられる。
本実施の形態に係る導電性樹脂組成物は、上述の複合導電性粒子1を導電材として含むことを特徴とする。複合導電性粒子1は、上述のように、高い導電性と高い充填性を有するものであり、これを導電材として含む導電性樹脂組成物は、上述の複合導電性粒子1の効果を引き継ぐことができる。すなわち、本発明の導電性組成物によれば、高い導電性を有する複合導電性粒子1を含むとともに、導電性樹脂組成物中において、複合導電性粒子1を高密度で充填させることができる。したがって、導電性の高い導電性樹脂組成物を提供することができる。
本実施の形態に係る導電性塗布物は、上記導電性樹脂組成物により形成された塗膜を基体上に有する塗布物である。したがって、この導電性塗布物は、高い導電性を備えたものとなる。
以下のようにして、実施例1に係る導電性粉末(複合導導電性粒子)を作製した。まず、第1粒子および第2粒子の材料として、シリカ粉末(商品名:「アドマファインSO-C6」、株式会社アドマテックス製)を準備した。なお、この粉末の特性は以下の通りであった。
比表面積:35922cm2/cm3
D10:0.69μm
D50:1.83μm。
水溶液1:硝酸銀6.75gと25%アンモニア水30mLをイオン交換水300mLに溶解させた水溶液
水溶液2:水酸化ナトリウム2.7gをイオン交換水300mLに溶解させた水溶液
水溶液3:ぶどう糖40.5gをイオン交換水300mLに溶解させた水溶液。
以下のようにして、実施例2に係る導電性粉末(複合導電性粒子)を作製した。まず、第1粒子および第2粒子の材料として、シリカ粉末(商品名:「アドマファインSO-C6」、株式会社アドマテックス製)を準備した。
水溶液1:硝酸銀1.75gと25%アンモニア水8mLをイオン交換水50mLに溶解させた水溶液
水溶液2:水酸化ナトリウム0.7gをイオン交換水50mLに溶解させた水溶液
水溶液3:ぶどう糖10.5gをイオン交換水50mLに溶解させた水溶液。
以下のようにして実施例3に係る導電性粉末(複合導電性粒子)を作製した。まず、第1粒子および第2粒子の材料として、シリカ粉末(商品名:「アドマファインSO-C6」、株式会社アドマテックス製)を準備した。
水溶液1:硝酸銀3.9gと25%アンモニア水18mLをイオン交換水110mLに溶解させた水溶液
水溶液2:水酸化ナトリウム1.5gをイオン交換水110mLに溶解させた水溶液
水溶液3:ぶどう糖23.6gをイオン交換水110mLに溶解させた水溶液。
以下のようにして実施例4に係る導電性粉末(複合導電性粒子)を作製した。まず、第1粒子および第2粒子の材料として、シリカ粉末(商品名:「アドマファインSO-C6」、株式会社アドマテックス製)を準備した。
水溶液1:硝酸銀10.5gと25%アンモニア水47mLをイオン交換水300mLに溶解させた水溶液
水溶液2:水酸化ナトリウム4.2gをイオン交換水300mLに溶解させた水溶液
水溶液3:ぶどう糖63gをイオン交換水300mLに溶解させた水溶液。
以下のようにして実施例5に係る導電性粉末(複合導電性粒子)を作製した。まず、第1粒子および第2粒子の材料として、株式会社アドマテックス製シリカ粉末を準備した。なお、この粉末の特性は以下の通りであった。
比表面積:7577cm2/cm3
D10:8.55μm
D50:16.24μm。
水溶液1:硫酸ニッケル14gをイオン交換水30mlに溶解させた水溶液
水溶液2:次亜リン酸ナトリウム3.1gをイオン交換水30mlに溶解させた水溶液
水溶液3:コハク酸ナトリウム3.0gをイオン交換水100mlに溶解させた水溶液。
めっき処理における翼周速度を20m/secとした以外は、実施例1と同様の方法を実施した。これにより、比較例1に係る導電性粉末を作製した。なお、この導電性粉末の色調は灰色であった。
実施例1および比較例1の各導電性粉末に関し、SEM観察を行った。具体的には、まず、カーボンテープ上に各導電性粉末を分散させた各試料を準備した。次に、走査型電子顕微鏡(製品名:「VE-7800」、株式会社キーエンス製)を用いて、加速電圧20kV、測定倍率5000倍の条件下で、各試料の反射電子像(電子画像)を撮影した。実施例1の導電性粉末のSEM写真を図5に、比較例1の導電性粉末のSEM写真を図6に示す。また、参考として、原料として用いたシリカ粉末のSEM写真を図7に示す。
実施例1~5および比較例1の各導電性粉末について、図5および図6に示すようなSEM観察を複数視野にて行った各SEM写真を解析することにより、各粒子の粒子径を求めた。実施例1においては、大きい粒子径を有する1つの粒子(第1導電性粒子)の表面に、これよりも小さい粒子径(第2導電性粒子)を有する複数の粒子が付着した複合導電性粒子が観察されたため、第1導電性粒子および第2導電性粒子のそれぞれの粒子径を求めることとした。その結果を表1の「粒子径(μm)」に示す。なお、各粒子径は、複数視野でのSEM観察により得られたSEM写真から任意に選択した50個の粒子の直径の平均値である。
実施例1~5の導電性粉末について、図5に示すようなSEM写真を解析することにより、第1導電性粒子に対する第2導電性粒子の付着率を求めた。なお、付着率の算出に関し、画像処理ソフトウェア(製品名:「WinROOF」、三谷商事株式会社)を用いて上述の算出方法に従った。その結果を表1の「付着率(%)」の欄に示す。なお、付着率は、任意に選択した50個の複合導電性粒子の平均値である。
実施例1~5および比較例1の各導電性粉末に関し、金属被覆率を算出した。具体的には、以下の手順で算出した。まず、原子吸光光度計による金属量の定量前の各導電性粉末の重量(酸溶液による溶解前の導電性粉末の重量)を測定した。次に、重量を測定した各導電性粉末を酸溶液に溶解させた各試料を準備した。次に、準備した各試料に関し、原子吸光光度計(製品名:「A-2000」、株式会社日立ハイテクフィールディング製)を用いて、各導電性粉末に含まれる金属量(各導電性粒子を構成するシリカ粒子の表面を被覆する金属量の総量に相当する)を測定した。そして、得られた金属の定量結果をもとに、下記式(2)により、各導電性粒子の金属被覆率(重量%)を算出した。この結果を表1の「被覆率(%)」の欄に示す。
金属被覆量(重量%)=W1/W2×100・・・(2)
(式(2)中、W1は金属被膜を構成する金属の重量を示し、W2は酸溶液による溶解前の導電性粉末の重量を示す)。
実施例1~5および比較例1の各導電性粉末の比抵抗を算出して、各導電性粉末の導電性を評価した。具体的には、各導電性粉末と樹脂(商品名:「ニッペアクリルオートクリヤースーパー」、日本ペイント社製)との配合率(導電性粉末:樹脂)が60vol%:40vol%になるように混練して、それぞれの導電性粉末を含有する樹脂組成物を作製した。
実施例1~5および比較例1の各導電性粉末のタップ密度を測定して、各導電性粉末の充填性を評価した。タップ密度はJIS Z2512:2012に準拠した方法で測定することができる。なお、タップ密度の測定には、タッピング式粉体減少度測定器(型式:「TPM-1」、筒井理化学器械株式会社製)を用いた。その結果を表2の「タップ密度(g/cm3)」に示す。タップ密度が大きいほど充填性に優れていることを示す。
実施例1の導電性粉末の断面を観察した。まず、エポキシ樹脂と導電性粉末を混合して硬化後、イオンミリング装置を用いて導電性粉末の断面観察用の試料を作製した。走査型電子顕微鏡(商品名:「SU8020」、株式会社日立ハイテクノロジー社製)を用いて、加速電圧50kV、測定倍率30000倍の条件下で、試料中の導電性粉末の断面を観察し反射電子像(電子画像)を撮影した。
Claims (6)
- 0.1μm以上50μm以下の粒子径を有する第1導電性粒子と、
前記第1導電性粒子の表面に付着する、50nm以上1000nm以下の粒子径を有する第2導電性粒子と、を備え、
前記第1導電性粒子は、第1粒子と、前記第1粒子の表面を被覆する第1金属被膜とからなり、
前記第2導電性粒子は、第2粒子と、前記第2粒子の表面を被覆する第2金属被膜とからなり、
前記第1導電性粒子の粒子径は前記第2導電性粒子の粒子径よりも大きく、
前記第2導電性粒子の前記第1導電性粒子に対する付着率は2%以上40%以下である、複合導電性粒子。 - 前記第1粒子および前記第2粒子は、それぞれシリカからなる、請求項1に記載の複合導電性粒子。
- 前記第1金属被膜および前記第2金属被膜は、それぞれ銀、金、銅、ニッケル、白金、錫およびこれらの合金からなる群より選ばれる少なくとも1種からなる、請求項1または請求項2に記載の複合導電性粒子。
- 前記第1導電性粒子は、有機酸を含む保護層を備える、請求項1から請求項3のいずれか1項に記載の複合導電性粒子。
- 請求項1から請求項4のいずれか1項に記載の複合導電性粒子を導電材として含む、導電性樹脂組成物。
- 請求項5に記載の導電性樹脂組成物により形成された塗膜を基体上に有する、導電性塗布物。
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