WO2014050156A1 - 導電性組成物及びそれを用いた導電性成形体 - Google Patents
導電性組成物及びそれを用いた導電性成形体 Download PDFInfo
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- WO2014050156A1 WO2014050156A1 PCT/JP2013/051792 JP2013051792W WO2014050156A1 WO 2014050156 A1 WO2014050156 A1 WO 2014050156A1 JP 2013051792 W JP2013051792 W JP 2013051792W WO 2014050156 A1 WO2014050156 A1 WO 2014050156A1
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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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
- H01B1/20—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29199—Material of the matrix
- H01L2224/2929—Material of the matrix with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—Fillers
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—Fillers
- H01L2224/29299—Base material
- H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
- H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/29339—Silver [Ag] as principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—Fillers
- H01L2224/29499—Shape or distribution of the fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12042—LASER
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/151—Die mounting substrate
- H01L2924/156—Material
- H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
- H01L2924/15788—Glasses, e.g. amorphous oxides, nitrides or fluorides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
Definitions
- the present invention relates to a molded article comprising a conductive composition useful for forming a conductive adhesive, an electrode, and the like, and a conductive part (conductive adhesive layer, electrode, wiring, etc.) formed by this conductive composition. It relates to (conductive molding).
- a conductive composition (conductive paste) containing conductive metal powder (conductive filler) such as silver paste is used for forming electrodes and circuits of electronic components and the like.
- the conductive paste containing a thermoplastic or thermosetting resin usually exhibits electrical conductivity by contact between the conductive fillers due to shrinkage of the resin used, and the presence of the resin. Adhesion or adhesion to the substrate is ensured. Therefore, in the conductive paste containing such a binder, in order to obtain sufficient conductivity, it is important to increase the contact area between the conductive metal powders. From such a viewpoint, attempts have been made to use metal flakes (flaked metal powder) as the conductive metal powder.
- Patent Document 1 discloses a conductive paste containing flaky silver powder and an organic resin.
- This document describes polyester resins, modified polyester resins (urethane-modified polyester resins, etc.), polyether urethane resins, polycarbonate urethane resins, vinyl chloride / vinyl acetate copolymers, epoxy resins, phenol resins, acrylic resins, polyamides as organic resins.
- a wide range of organic resins such as imide, nitrocellulose, cellulose acetate acetate butyrate, cellulose acetate propionate, etc. are exemplified, and in particular, polyester resin and urethane-modified polyester resin are used in terms of flex resistance in the examples. Yes.
- Patent Document 2 discloses flaky silver powder in which the average particle diameter and the BET specific surface area have a specific relationship. And in this document, epoxy resin, acrylic resin, polyester resin, polyimide resin, polyurethane resin, phenoxy resin, silicone resin, etc. are exemplified as the resin used for the conductive paste, and polyester resin is used in the examples. .
- an object of the present invention is to provide a conductive composition capable of realizing excellent conductivity even when a resin component is included, and a molded body having a conductive portion formed of the conductive composition. .
- Another object of the present invention is to provide a conductive composition capable of improving or improving conductivity without impairing adhesion or adhesion to a substrate, and a molded article having a conductive portion formed from the conductive composition. It is to provide.
- Still another object of the present invention is to provide a molded article provided with a conductive adhesive excellent in conductivity and heat dissipation and a bonding substrate directly bonded by this conductive adhesive.
- the present inventors have combined metal nanoparticles and a specific resin component with respect to metal flakes (flaked metal powder) in the conductive composition, High conductivity is obtained, and despite having such high conductivity, excellent adhesion or adhesion to the base material can be compatible, and furthermore, high heat dissipation is required.
- the inventors have found that sufficient conductivity and heat dissipation (and further adhesion) can be secured even in the use of conductive adhesives, and the present invention has been completed.
- the present invention is a composition comprising a conductive metal powder and a resin component, wherein the conductive metal powder includes metal flakes and metal nanoparticles, and the resin component is an aromatic amine skeleton (or aromatic amine or An electrically conductive composition comprising an aromatic amine-derived skeleton) is provided.
- the metal flakes may have a crystal structure in which a metal (or metal crystal) is grown (or two-dimensionally) in the form of flakes (or crystal growth).
- the metal flake is a metal having a value X represented by the following formula of 20% or less when the diffraction integrated intensity of the (111) plane and (200) plane in X-ray diffraction is I 111 and I 200 , respectively. Flakes may be used.
- the resin component may be a thermosetting resin component.
- the resin component is composed of a thermosetting resin (or a thermosetting resin precursor) and a curing agent (or a crosslinking agent), and the thermosetting resin and / or the curing agent has an aromatic amine skeleton.
- the thermosetting resin component may be included.
- the curing agent may be composed of an aromatic amine curing agent.
- the resin component is an epoxy resin component containing an epoxy resin and a curing agent composed of an aromatic amine curing agent, or composed of a polyisocyanate compound and an aromatic amine curing agent. It may be a polyisocyanate resin component containing a curing agent.
- the resin component may be an epoxy resin component including an epoxy resin having an epoxy equivalent of 600 g / eq or less and a curing agent composed of an aromatic amine-based curing agent.
- the aromatic amine curing agent may be, for example, an aromatic amine curing agent having a structure in which an amino group is directly substituted on the aromatic ring.
- the conductive composition of the present invention may be a conductive adhesive (for example, a die bond paste).
- a metal substrate for example, a lead frame formed of metal (copper, copper alloy, etc.), a lead frame formed of metal and further plated, etc.] and a semiconductor substrate
- a conductive adhesive (die bond paste) for adhering to (a semiconductor chip, for example, a semiconductor substrate, a semiconductor chip having a metal film formed on the semiconductor substrate) may be used.
- a semiconductor chip on which the metal film is formed it may be used as a conductive adhesive for bonding the lead frame and the metal film of the semiconductor chip.
- the present invention further provides a molded body (conductive molded body) having at least a conductive portion (or conductive film) formed of the conductive composition.
- a molded body (electrical / electronic component, etc.) is a molding provided with a joining base material composed of two base materials and a conductive adhesive that is interposed between the base materials and adheres the two base materials. It may be a molded body in which the conductive adhesive is a conductive portion formed of the conductive composition.
- a molded body includes, for example, a base material (such as a lead frame) formed of a metal and a base material (such as a semiconductor chip) formed of a semiconductor, and the conductive material interposed and bonded between these base materials. It may be formed with the composition.
- the present invention is a conductive molded body having at least a conductive part (or conductive film) formed of a conductive composition containing metal flakes, metal nanoparticles, and a resin component,
- a conductive part or conductive film formed of a conductive composition containing metal flakes, metal nanoparticles, and a resin component
- the value X represented by the following formula is 25% or less (particularly 20% or less, particularly preferably The conductive molded body is 10% or less.
- the conductive molded body is a molded body provided with a joining base material composed of two base materials and a conductive adhesive that is interposed between the base materials and adheres the two base materials.
- the conductive adhesive is formed of a conductive composition containing metal flakes, metal nanoparticles, and a resin component, and the value X in the conductive adhesive is 25% or less (particularly 20% or less, particularly preferably 10%). The following may be used.
- the value of X may be measured on the side in contact with the base material (base material side) or on the surface side.
- the X value may be slightly different depending on the measurement site, the X value is preferably within the above range even in such a case.
- the conductive composition is particularly a conductive composition including metal flakes, metal nanoparticles, and a resin component (a resin component that may have an aromatic amine skeleton). It is not limited, and it is not necessary to have the same composition as the conductive composition.
- a resin component that does not have an aromatic amine skeleton as a resin component for example, a thermosetting resin component such as an epoxy resin component). May be used.
- at least the metal flakes and metal nanoparticles may be the same components as the conductive composition, and in a more preferred embodiment, the resin component is also the same resin component as described above (that is, a resin component having an aromatic amine skeleton). ).
- the metal flake may be a metal flake having a crystal structure in which a metal (or metal crystal) is grown (or two-dimensionally) in the form of flakes (or crystal growth). It may be metal flakes (particularly 20% or less, particularly preferably 10% or less). That is, by using such metal flakes, it is possible to easily form a conductive portion or a conductive adhesive that keeps the crystal state of the metal flakes surprisingly in a conductive molded body.
- the conductive composition of the present invention excellent conductivity can be realized in spite of including a resin component as a binder. In addition, such improvement or improvement in conductivity can be realized without impairing adhesion or adhesion to the substrate. Moreover, since the electroconductive composition of this invention is excellent in electroconductivity and heat dissipation (thermal conductivity), and also can ensure sufficient adhesiveness, it is especially useful as a conductive adhesive.
- the conductive composition of the present invention is composed of a specific conductive metal powder and a specific resin component.
- the conductive metal powder contains at least metal flakes (flaky metal powder, plate-like metal powder, scale-like metal powder) and metal nanoparticles.
- metal (metal flakes) examples of the metal (metal atom) constituting the metal flake include transition metals (for example, periodic table group 4 metals such as titanium and zirconium; periodic table group 5 metals such as vanadium and niobium; periodicity such as molybdenum and tungsten).
- transition metals for example, periodic table group 4 metals such as titanium and zirconium; periodic table group 5 metals such as vanadium and niobium; periodicity such as molybdenum and tungsten.
- Group 6 metal Periodic table Group 7 metal such as manganese, rhenium
- Group 8-10 metal of periodic table such as iron, nickel, cobalt, ruthenium, rhodium, palladium, iridium, platinum; Copper, silver, gold, etc.
- Periodic table group 11 metals Periodic table group 11 metals
- periodic table group 12 metals eg, zinc, cadmium, etc.
- periodic table group 13 metals eg, aluminum, gallium, indium, etc.
- periodic table group 14 metals eg, Germanium, tin, lead, etc.
- periodic table group 15 metals for example, antimony, bismuth, etc.
- a metal may be individual or may combine 2 or more types.
- Typical metals include Group 8-10 metals of the periodic table (iron, nickel, rhodium, palladium, platinum, etc.), Group 11 metals of the periodic table (copper, silver, gold, etc.), Group 13 metals of the periodic table ( Aluminum), periodic table group 14 metals (tin, etc.).
- the metal is in the form of a metal alloy, a compound of metal and nonmetal (for example, metal oxide, metal hydroxide, metal sulfide, metal carbide, metal nitride, metal boride, etc.) There may be.
- the metal is often a simple metal or a metal alloy.
- the metal is preferably a metal (for example, a simple metal or a metal alloy) containing at least a noble metal such as silver (particularly a Group 11 metal in the periodic table), particularly a single noble metal (for example, silver alone).
- a metal for example, a simple metal or a metal alloy
- a noble metal such as silver (particularly a Group 11 metal in the periodic table), particularly a single noble metal (for example, silver alone).
- metal flakes can be used alone or in combination of two or more.
- the metal flake is not particularly limited, but (i) a metal flake having a crystal structure (crystal structure 1) in which a metal (or metal crystal) is grown (or crystal grown) in a flake shape (or two-dimensionally), (ii) Any of flaked (or flattened) metal fine particles (or spherical fine particles) having a crystal structure (crystal structure 2) in which a large number of crystallites are assembled may be used.
- the metal flake (i) mainly has a crystal structure in which a single crystal is grown to a flaky metal, whereas the metal flake (ii) usually has a crystal in which a large number of crystallites are assembled.
- the fine metal particles (or aggregates thereof) having a structure the flakes also mainly have a crystal structure in which a large number of crystallites are assembled.
- the metal flake (ii) is physically formed into flakes, fine irregularities are easily generated on the metal surface.
- the metal flake (i) mainly having the crystal structure 1 is preferable because it is smaller than the crystal structure 2 in terms of resistance at the crystal grain boundary, but is a plate that occupies most of the flake area in the crystal plane.
- the surface for example, (111) plane mainly in the case of a face-centered cubic lattice such as silver flakes] has low surface energy and metal bonding at the interface hardly occurs, sufficient electrical conductivity cannot be secured. There is.
- the metal flake (ii) is caused by the crystal structure 2 and the resistance at the crystal grain boundary is larger than that of the crystal structure 1.
- the sintering at the metal flake interface is caused by fine irregularities on the surface. In comparison, it is easier to compare with the crystal structure 1 and a reduction in resistance due to metal bonding can be expected.
- the metal flakes may be appropriately selected according to the desired use and conductivity, but in the present invention, the metal flakes (i) may be particularly preferably used. Even with such metal flakes (i), by combining with metal nanoparticles and resin components described later, sufficient contact between the metal flakes can be ensured, or high conductivity can be ensured. These components can act synergistically to achieve even higher conductivity than when metal flake (ii) is used.
- the degree of crystallinity in the metal flakes can be estimated using the diffraction intensity in X-ray diffraction as an index.
- the diffraction intensity in X-ray diffraction in the powder X-ray diffraction method, in the metal flake having the crystal structure 1 to which anisotropy (orientation) is imparted by crystal growth, the diffraction with respect to the plane or the plate surface mainly corresponds to the (111) plane and has a large intensity.
- the diffraction with respect to the surface forming the thickness mainly corresponds to the (200) surface, and its intensity appears extremely small.
- metal flakes having 0 to 9%) may be mainly metal flakes having crystal structure 1 (that is, metal flakes (i)).
- the value of the above X is maintained even after molding (for example, after the conductive composition is cured) in the conductive sites and conductive adhesives described later.
- An electroconductive molded object can be obtained efficiently.
- the value of X is usually more than 25% (for example, 27 to 40%), preferably about 30% or more (for example, 32 to 40%). It may be about 40%.
- the metal flakes commercially available products may be used, or those synthesized by a conventional method may be used.
- the metal flakes (i) are produced using the production methods described in Japanese Patent No. 3429985, Japanese Patent No. 4144856, Japanese Patent No. 4399799, Japanese Unexamined Patent Publication No. 2009-144188, and the like.
- metal flakes described in these documents can be used.
- the average particle diameter of the metal flakes is, for example, 0.1 to 20 ⁇ m, preferably 0.3 to 15 ⁇ m (for example, 0.5 to 12 ⁇ m), more preferably 0.7 to 10 ⁇ m (for example, 0.8 to 7 ⁇ m). It may be about 1 to 10 ⁇ m.
- the average particle size of the metal flakes can be measured using, for example, a laser diffraction / scattering particle size distribution measurement method. In such a measurement method, the average particle diameter (center particle diameter) is measured as a volume-based value.
- the average thickness of the metal flakes may be, for example, 5 to 1000 nm, preferably 20 to 500 nm, more preferably 50 to 300 nm, and usually about 10 to 300 nm.
- the aspect ratio (average particle diameter / average thickness) of the metal flakes may be, for example, about 5 to 100, preferably about 7 to 50, and more preferably about 10 to 30.
- the BET specific surface area of the metal flakes can be selected from the range of about 0.3 to 7 m 2 / g, for example, 0.5 to 6 m 2 / g, preferably 1 to 5 m 2 / g, more preferably 1.2 to It may be about 4 m 2 / g, and usually about 1 to 5 m 2 / g.
- the tap density of the metal flakes can be selected from the range of about 0.1 to 7 g / cm 3 (for example, 0.2 to 6 g / cm 3 ), for example, 0.3 to 5 g / cm 3 , preferably 0.5 May be about 4.5 g / cm 3 , more preferably about 1 to 4 g / cm 3 , and usually about 1.2 to 4 g / cm 3 (eg, 1.5 to 3.5 g / cm 3 ). May be.
- Metal nanoparticles Metal flakes are used in combination with metal nanoparticles. By combining metal flakes with such metal nanoparticles (and with a specific resin component), high conductivity and adhesion can be realized efficiently. The reason for this is not clear, but the metal nanoparticle intervenes between the metal flakes to physically increase the contact area between the metal flakes or form metal bonds by sintering the metal nanoparticles. This is also considered to be a factor. In particular, since such an effect has a feature of supplementing the contact at the metal interface, it is often remarkable in combination with the metal flake having the single crystal structure as described above. However, even if metal flakes and metal nanoparticles are simply combined, sufficient contact may not be ensured, and high conductivity can be realized by further combining specific resin components described later.
- the form of the metal nanoparticles may be non-flaked and may be fibrous, but may be usually spherical (or almost spherical).
- the aspect ratio of the metal nanoparticles (spherical metal nanoparticles) may be, for example, 3 or less (for example, 1 to 2.5), preferably 2 or less (for example, 1 to 1.5).
- the metal which comprises a metal nanoparticle is the same as the metal described in the item of the said metal flakes.
- the metal flakes and the metal nanoparticles may be the same or different from each other.
- the metal nanoparticles may be used alone or in combination of two or more.
- the average particle diameter (D50) of the metal nanoparticles may be nano-sized, but can be selected from a range of about 1 to 800 nm (for example, 2 to 600 nm), for example, 3 to 500 nm (for example, 5 to 300 nm), Preferably, it may be about 5 to 200 nm (eg, 7 to 180 nm), more preferably about 10 to 150 nm (eg, 20 to 120 nm), and usually 1 to 300 nm (eg, 2 to 200 nm, preferably 3 to 150 nm, More preferably, it may be about 4 to 100 nm.
- the average particle size can be measured using an electron microscope (such as a transmission electron microscope or a scanning electron microscope) or a laser diffraction / scattering particle size distribution measurement method.
- a commercial item may be used for a metal nanoparticle, and what was synthesize
- commercially available products include Sylbest C-34, Sylbest H-1, Sylbest E-20, Mitsui Mining & Mining ST-M, SPH02J, Superfine Silver Powder-1, DOWA Electronics Co., Ltd., Silver Nanoparticle dry powder-1, Silver nanoparticle dry powder-2, G-13, G-35, GS-36 manufactured by DOWA High-Tech Co., Ltd., AgC-101, AgC-111, AgC-114, AgC- manufactured by Fukuda Metal Foil Powder Industry 141, AgC-152, AgC-153, AgC-154, and the like.
- 97/3 to 15/85 for example, 96/4 to 20/80
- 95/5 to 25/75 for example, 93/7 to 27/73
- 90/10 to It may be about 30/70 (for example, 88/12 to 35/65), particularly about 85/15 to 40/60 (for example, 80/20 to 45/55), and usually about 80/20 to 40/60. It may be.
- the resin component constituting the conductive composition has an aromatic amine skeleton (or a skeleton derived from an aromatic amine).
- an aromatic amine skeleton or a skeleton derived from an aromatic amine.
- thermoplastic resins or thermoplastic resin components, for example, condensation resins such as polyamide resins and polyester resins; addition polymerization resins such as (meth) acrylic resins), thermosetting resin components, and the like. Although there may be, in this invention, you may use a thermosetting resin component suitably.
- thermosetting resin or thermosetting resin component
- examples of the thermosetting resin (or thermosetting resin component) include epoxy resin, phenol resin, amino resin, polyurethane resin (polyisocyanate compound or polyisocyanate resin), (meth) acrylic resin, and polyimide resin. It is done.
- the resin component contains an aromatic amine skeleton depending on the form of the resin.
- the aromatic amine skeleton may have a free amino group or may be contained in the resin monomer.
- a resin having an aromatic amine as a polymerization component (or monomer) for example, aromatic diamine (the aromatic amine system exemplified in the section of the epoxy resin component described later)
- Addition polymerization resin such as (meth) acrylic resin having a polymerization component such as phenyl.
- thermosetting resin component a thermosetting resin (for example, glycidylamine-type aromatic epoxy resin, aniline resin, or the like) having an aromatic amine as a polymerization component (or monomer) or cured Thermosetting resin component containing an aromatic amine as an agent (or cross-linking agent), curing accelerator, or initiator
- thermosetting resin for example, epoxy resin, phenol resin, polyisocyanate compound, etc.
- aromatic Thermosetting resin components containing a curing agent (or curing accelerator) composed of an aromatic amine-based curing agent for example, a curing agent of an epoxy resin, a phenol resin or a polyisocyanate compound
- the resin component having an aromatic amine skeleton may be used alone or in combination of two or more.
- the ratio of the aromatic amine skeleton depends on the form of the resin, but is, for example, 1% by weight or more of the total resin component (for example, 2 To 100% by weight), preferably 3% by weight or more (eg, 4 to 90% by weight), and more preferably about 5% by weight or more (eg, 7 to 80% by weight).
- the ratio of the aromatic amine skeleton to the entire thermosetting resin component is 3% by weight or more of the entire resin component (for example, it may be about 4 to 100% by weight), preferably about 5% by weight or more (for example, 7 to 90% by weight), more preferably about 10% by weight or more (for example, 15 to 80% by weight).
- a typical resin component includes a thermosetting resin (or a thermosetting resin precursor) and a curing agent (or a crosslinking agent), and the thermosetting resin and / or the curing agent includes an aromatic amine skeleton.
- a curable resin component is included.
- a thermosetting resin component including a thermosetting resin (for example, epoxy resin, polyisocyanate compound) and a curing agent composed of an aromatic amine-based curing agent (such as a compound described later) is preferable. When an aromatic amine curing agent is used, high conductivity can be realized more efficiently.
- the ratio of the aromatic amine-based curing agent depends on the type of the thermosetting resin, but is, for example, 0.1 to 800 parts by weight with respect to 100 parts by weight of the thermosetting resin, preferably The amount may be about 0.5 to 500 parts by weight, more preferably about 1 to 300 parts by weight (for example, 2 to 200 parts by weight), and particularly about 3 to 150 parts by weight (for example, 5 to 100 parts by weight).
- epoxy resin component As a typical epoxy resin component, an epoxy resin component containing an epoxy resin and a curing agent composed of an aromatic amine-based curing agent is included.
- the epoxy resin is not particularly limited, and is a monofunctional epoxy resin [for example, glycidyl ethers (for example, aromatic monoglycidyl ethers such as phenyl glycidyl ether and o-phenylphenyl glycidyl ether), cycloalkene oxides (for example, 4 -Vinyl epoxycyclohexane, epoxyhexahydrophthalic acid dialkyl ester, etc.)] and any other polyfunctional epoxy resin may be used, but it can usually be constructed using at least a polyfunctional epoxy resin (or epoxy compound).
- glycidyl ethers for example, aromatic monoglycidyl ethers such as phenyl glycidyl ether and o-phenylphenyl glycidyl ether
- cycloalkene oxides for example, 4 -Vinyl epoxycyclohexane, epoxyhexahydrophthalic acid dialkyl ester, etc.
- the epoxy resin may be any of a glycidyl ether type, a glycidyl amine type, a glycidyl ester type, an alicyclic type (epoxy resin having an epoxy cycloalkane skeleton), and the like.
- the number of epoxy groups may be two or more, for example, 2 to 150 (for example, 2 to 120), preferably 2 to 100 (for example, 2 to 80), and more preferably May be about 2 to 50 (for example, 2 to 30).
- Specific polyfunctional epoxy resins include aliphatic epoxy resins (polyfunctional aliphatic epoxy resins) and alicyclic epoxy resins [for example, bifunctional alicyclic epoxy resins. (Eg, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate), trifunctional or higher alicyclic epoxy resins (eg, 2,2-bis (hydroxymethyl) -1-butanol and 3, 4-alkane tri- or hexa-ols such as triesters with epoxycyclohexanecarboxylic acid, etc.], aromatic epoxy resins, nitrogen-containing epoxy resins (nitrogen-containing polyfunctional) Epoxy resin such as triglycidyl isocyanurate) .
- aliphatic epoxy resins polyfunctional aliphatic epoxy resins
- alicyclic epoxy resins for example, bifunctional alicyclic epoxy resins.
- trifunctional or higher alicyclic epoxy resins eg, 2,2-bis (hydroxymethyl)
- aliphatic epoxy resins include bifunctional aliphatic epoxy resins [for example, aliphatic diglycidyl ethers (eg, alkanediol diglycidyl ethers such as butanediol diglycidyl ether and neopentyl glycol diglycidyl ether; polyethylene glycol diglycidyl).
- bifunctional aliphatic epoxy resins for example, aliphatic diglycidyl ethers (eg, alkanediol diglycidyl ethers such as butanediol diglycidyl ether and neopentyl glycol diglycidyl ether; polyethylene glycol diglycidyl).
- poly C 2-4 alkanediol diglycidyl ether such as polypropylene glycol diglycidyl ether), diglycidyl ether type bifunctional aliphatic epoxy resin such as cyclohexanedimethanol diglycidyl ether; hydrogenated aromatic dicarboxylic acid (for example, , Tetrahydrophthalic acid, hexahydrophthalic acid, etc.) diglycidyl ester, dimer acid glycidyl ester glycidyl ester type bifunctional aliphatic epoxy resin], Sankan Or more aliphatic epoxy resins (e.g., trimethylol propane triglycidyl ether, glycerol triglycidyl ether, trimethylolpropane or hexa glycidyl ethers of alkane tri to hexa-ol, such as pentaerythritol or tetraglycidyl ether).
- aromatic epoxy resin for example, glycidyl ether type aromatic epoxy resin ⁇ eg, polyglycidyloxyarenes [eg, diglycidyloxynaphthalene (eg, 1,5-di (glycidyloxy) naphthalene, 1,6-diethyl)] (Glycidyloxy) naphthalene, 2,6-di (glycidyloxy) naphthalene, 2,7-di (glycidyloxy) naphthalene, 2,7-di (2-methyl-2,3-epoxypropyloxy) naphthalene, etc.)
- Polyglycidyloxynaphthalenes such as 2,2′-diglycidyloxybinaphthalene]; polyglycidyloxyarenes (such as the polyglycidyloxynaphthalene exemplified above) are directly bonded or linked (for example, methylene group, ethylene group).
- Linked compounds for example, poly (diglycidyloxynaphthyl) C 1 -1, such as 1,1′-methylenebis (2,7-diglycidyloxynaphthalene) or bis (2,7-diglycidyloxynaphthyl) methane.
- tri to octa (glycidyloxyaryl) alkanes for example, 1,1,2,2-tetrakis (4-glycidyloxyphenyl) ethane, 1,1,1-tris (glycidyloxyphenyl) methane, To hexa (glycidyloxyphenyl) C 1-10 alkane]; bisphenol type epoxy resin; novolac type epoxy resin; diglycidyl aniline, etc. ⁇ , glycidyl ester type aromatic epoxy resin [eg, aromatic dicarboxylic acid (phthalic acid, etc.) Diglycidyl ester, etc.], glycidyl Type aromatic epoxy resins [eg, N, N-diglycidylaniline; tetra- to octaglycidyl polyamines such as tetraglycidyldiaminodiphenylmethane, tetraglycidylmetaxylylenediamine;
- Examples of the bisphenol type epoxy resin include diglycidyl ethers of bisphenols or adducts thereof (for example, C 2-4 alkylene oxides such as ethylene oxide and propylene oxide).
- Examples of bisphenols include biphenols; bis (hydroxyphenyl) C 1-10 alkanes such as bisphenol A, bisphenol B, bisphenol E, and bisphenol F; 2,2-bis (3-methyl-4-hydroxyphenyl) propane; Bis (hydroxy C 1-10 alkylphenyl) C 1-10 alkanes such as bisphenol G; bis (hydroxy C 6-10 arylphenyl) C 1-10 alkanes such as bisphenol PH; bis (hydroxys such as bisphenol Z and bisphenol TMC Phenyl) C 5-10 cycloalkane; bisphenol AP, bisphenol BP; bisphenol AF; bisphenol S; bisphenol M; bisphenol P and the like.
- the number of moles of alkylene oxide added relative to 1 mol of hydroxyl group of bisphenol is, for example, 1 mol or more (eg, 1 to 20 mol), preferably 1 to 15 mol, more preferably May be about 1 to 10 moles.
- the phenol compound (compound having a phenolic hydroxyl group) may be phenols [eg, phenol; alkylphenol (eg, cresol, ethylphenol, s-butylphenol, t-butylphenol, 1,1 , 3,3-tetramethylbutylphenol, decylphenol, dodecylphenol, etc., C 1-20 alkylphenol, preferably C 1-12 alkylphenol, more preferably C1-4 alkylphenol), aralkylphenol (eg 1,1-dimethyl) -1-C 6-10 aryl C 1-10 alkylphenol) substituted phenols, such as such as phenyl methyl phenol], naphthols (e.g., naphthols and the like), bisphenols [eg, phenol; alkylphenol (eg, cresol, ethylphenol, s-butylphenol, t-butylphenol, 1,1 , 3,3-tetramethylbutyl
- the novolac resin may be a modified novolac resin.
- the novolak resin has a non-phenolic compound skeleton [for example, an araliphatic skeleton (for example, a C 6-10 arene di C 1-4 alkylene skeleton such as a xylylene skeleton), an alicyclic skeleton (for example, a dicyclopentadiene skeleton, etc.
- Typical novolak-type epoxy resins include, for example, novolak-type epoxy resins having a phenolic compound as a polymerization component [for example, phenol novolak-type epoxy resins, alkylphenol novolak-type epoxy resins (for example, cresol novolak-type epoxy resins), naphthol, and the like.
- Novolak type epoxy resins bisphenol novolak type epoxy resins (for example, bisphenol A novolak type epoxy resins, bisphenol F novolak type epoxy resins, etc.), etc., modified novolak type epoxy resins having a phenolic compound as a polymerization component
- aralkyl novolak type Epoxy resin for example, xylylene skeleton-containing phenol novolac resin
- dicyclopentadiene skeleton-containing novolak type epoxy resin for example, dicyclopentadiene resin
- tantadiene skeleton-containing phenol novolac epoxy resin biphenyl skeleton-containing novolak epoxy resin (for example, biphenyl skeleton-containing phenol novolac epoxy resin), brominated novolak-type epoxy resin (for example, brominated phenol novolak-type epoxy resin), etc.
- Modified novolak-type epoxy resin having a phenolic compound as a polymerization component for example, aralkyl novolak type Ep
- the number average molecular weight of the novolak type epoxy resin may be, for example, about 1,000 to 1,000,000, preferably about 5,000 to 500,000, and more preferably about 10,000 to 100,000. .
- Epoxies may be used alone or in combination of two or more.
- the epoxy equivalent of the epoxy resin is not particularly limited and can be selected from the range of about 800 g / eq or less (for example, 50 to 750 g / eq), but for example, 700 g / eq or less (for example, 70 to 650 g / eq), preferably May be about 600 g / eq or less (for example, 80 to 550 g / eq), particularly about 500 g / eq or less (for example, 100 to 450 g / eq).
- the epoxy resin component contains a curing agent (epoxy resin curing agent) composed of an aromatic amine-based curing agent in addition to the epoxy resin (and other epoxy resin as necessary) as a main agent.
- a curing agent epoxy resin curing agent
- aromatic amine-based curing agent an aromatic amine-based curing agent in addition to the epoxy resin (and other epoxy resin as necessary) as a main agent.
- aromatic amine curing agent examples include polyamino arenes (eg, diamino arenes such as paraphenylene diamine and metaphenylene diamine, preferably diamino C 6-10 arenes), polyamino-alkyl arenes (eg, diethyl toluene diamine and the like).
- polyamino arenes eg, diamino arenes such as paraphenylene diamine and metaphenylene diamine, preferably diamino C 6-10 arenes
- polyamino-alkyl arenes eg, diethyl toluene diamine and the like.
- Diamino-alkyl arenes preferably diamino-mono to tri C 1-4 alkyl C 6-10 arenes
- poly (aminoalkyl) arenes eg di (aminoalkyl) arenes such as xylylenediamine, preferably di (amino) C 1-4 alkyl) C 6-10 arene
- poly (aminoaryl) alkanes eg di (aminoaryl) alkanes such as diaminodiphenylmethane, preferably di (aminoC 6-10 aryl) C 1-6 alkanes
- Poly ( Amino (alkylaryl) alkanes such as di (amino-alkylaryl) alkanes such as 4,4′-methylenebis (2-ethyl-6-methylaniline), preferably di (amino-C 1-4 alkylC 6- 10 aryl) C 1-6 alkane), bis (aminoarylalkyl) arene (eg
- Aromatic amine curing agents may be used alone or in combination of two or more.
- aromatic amines in which an amino group is directly substituted on the aromatic ring for example, poly (aminoaryl) alkane, di (aminoaryl) ether, etc.] are preferable.
- curing agent contains the aromatic amine type hardening
- examples of other curing agents include non-aromatic amine-based curing agents ⁇ for example, aliphatic amine-based curing agents (for example, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, etc.
- alicyclic amine curing agents eg mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, 3,9-bis (3-aminopropyl)- Monocyclic aliphatic polyamines such as 2,4,8,10-tetraoxaspiro [5.5] undecane; bridged cyclic polyamines such as norbornanediamine
- imidazole-based curing agents [imidazoles (for example, 2-methyl Imidazole, 2-phenylimidazole, 2 Alkyl imidazoles such as heptadecylimidazole and 2-ethyl-4-methylimidazole; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-benzyl- Aryl imidazoles such as 2-phenylimidazole), salts of imidazoles (for example, 2-methyl Imidazo
- the ratio of the curing agent depends on the type of the curing agent and the combination of the epoxy resin and the curing agent, but for example, 0.1 to 500 with respect to 100 parts by weight of the epoxy resin. Parts by weight, preferably 1 to 300 parts by weight, more preferably about 2 to 200 parts by weight (eg 3 to 100 parts by weight), usually 4 to 80 parts by weight (eg 5 to 60 parts by weight) It may be a degree.
- the proportion of the curing agent can be appropriately selected depending on the epoxy equivalent of the epoxy resin depending on the type of the curing agent.
- the functional group (amino) of the curing agent with respect to 1 equivalent of the epoxy group of the epoxy resin. Group) may be, for example, 0.1 to 4.0 equivalents, preferably 0.3 to 2.0 equivalents, and more preferably 0.5 to 1.5 equivalents.
- the epoxy resin component may contain a curing accelerator.
- the curing accelerator is not particularly limited, and is a conventional curing accelerator for epoxy resins, such as phosphines (for example, ethylphosphine, propylphosphine, phenylphosphine, triphenylphosphine, trialkylphosphine, etc.), amines ( For example, piperidine, triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, triethylenediamine, tris (dimethylaminomethyl) phenol, secondary or tertiary amines such as N, N-dimethylpiperazine or salts thereof, etc. Is mentioned.
- the above-described curing agents for example, imidazoles
- a hardening accelerator can be used individually or in combination of 2 or more types.
- the ratio of the curing accelerator is not particularly limited, and depends on the combination with an epoxy resin or a curing agent. For example, 0.01 to 100 parts by weight, preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin. It may be about 80 parts by weight, more preferably about 0.1 to 50 parts by weight, and usually about 0.5 to 30 parts by weight (for example, 1 to 25 parts by weight).
- Polyisocyanate resin component As a typical polyisocyanate resin component, a polyisocyanate resin component containing a polyisocyanate compound and a curing agent composed of an aromatic amine-based curing agent is included.
- Polyisocyanate compounds include polyisocyanates and modified polyisocyanates (for example, blocked isocyanates [blocking agents (for example, pyrazole, alkylpyrazole (3-methylpyrazole, etc.), halopyrazole (3-chloropyrazole, etc.), etc.
- blocked isocyanates for example, pyrazole, alkylpyrazole (3-methylpyrazole, etc.), halopyrazole (3-chloropyrazole, etc.
- alkanediols ethylene glycol, propylene glycol, etc.
- di to tetraalkanediols diethylene glycol, etc.
- Polyisocyanates can be roughly classified into, for example, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and the like.
- Aliphatic polyisocyanates include, for example, aliphatic diisocyanates ⁇ eg, alkane diisocyanates [eg, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, C 2-20 alkane-diisocyanate, such as lysine diisocyanate, preferably C 4-12 alkane-diisocyanate, etc.] etc.] Aliphatic polyisocyanates having 3 or more isocyanate groups (eg 1,3,6-hexamethylene) Triisocyanate, triisocyanate such as 1,4,8-triisocyanatooctane) and the like.
- alkane diisocyanates eg, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, C
- alicyclic polyisocyanate examples include alicyclic diisocyanate ⁇ cycloalkane diisocyanate (for example, C 5-8 cycloalkane-diisocyanate such as methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc.)
- Isocyanatoalkylcycloalkane isocyanates eg, isocyanato C 1-6 alkyl-C 5-10 cycloalkane-isocyanates such as isophorone diisocyanate), di (isocyanatoalkyl) cycloalkanes [eg 1,4-di (isocyanato di etc.) cyclohexane (isocyanato C 1-6 alkyl) C 5-10 cycloalkane, di (isocyanatomethyl cycloalkyl) alkanes [e.g., 4,4'-methylene-bis
- araliphatic polyisocyanate examples include di (isocyanatoalkyl) arene [for example, bis (isocyanato C 1-6 alkyl) C 6-12 arene such as xylylene diisocyanate, tetramethyl xylylene diisocyanate, etc.] Aliphatic diisocyanates are mentioned.
- Aromatic polyisocyanates include aromatic diisocyanates ⁇ eg, arene diisocyanates [eg C 6-12 arene diisocyanates such as o-, m- or p-phenylene diisocyanate, chlorophenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, etc.]
- Bis (isocyanato C 6-10 aryl) C 1 such as di (isocyanatoaryl) alkane [for example, diphenylmethane diisocyanate (MDI) (2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, etc.), tolidine diisocyanate, etc.
- alkanes preferably bis (isocyanato C 6-8 aryl) C 1-6 alkanes etc.], poly (isocyanatoaryl) ethers (eg , Di (isocyanatophenyl) ether, etc.), poly (isocyanatoaryl) sulfone (eg, di (isocyanatophenyl) sulfone etc.), etc. ⁇ aromatic polyisocyanates having 3 or more isocyanate groups (eg, 4 , 4′-diphenylmethane-2,2 ′, 5,5′-tetraisocyanate, etc.) and the like.
- isocyanate groups eg, 4 , 4′-diphenylmethane-2,2 ′, 5,5′-tetraisocyanate, etc.
- polyisocyanate compounds may be used alone or in combination of two or more.
- the polyisocyanate compound is often composed of at least a diisocyanate compound.
- the content of isocyanate groups may be, for example, about 3 to 70% by weight, preferably about 5 to 60% by weight, and more preferably about 7 to 50% by weight.
- the polyisocyanate resin component contains a curing agent (or a crosslinking agent or a polyisocyanate curing agent) composed of an aromatic amine curing agent in addition to the polyisocyanate compound as the main agent.
- a curing agent or a crosslinking agent or a polyisocyanate curing agent
- aromatic amine-based curing agent examples include the curing agents exemplified in the section of the epoxy resin component, and preferred embodiments are the same as described above.
- Aromatic amine curing agents may be used alone or in combination of two or more.
- the curing agent contains an aromatic amine-based curing agent
- other curing agents for example, non-aromatic amine-based curing agents (non-aromatic amine-based curing agents exemplified in the section of the epoxy resin component, etc. ), Polyol compounds, etc.].
- the proportion of the curing agent depends on the type of the curing agent and the combination of the polyisocyanate compound and the curing agent, but is, for example, 0.1% with respect to 100 parts by weight of the polyisocyanate compound. It may be about 500 parts by weight, preferably 1 to 300 parts by weight, more preferably about 2 to 200 parts by weight (eg 3 to 100 parts by weight), and usually 4 to 80 parts by weight (eg 5 to 60 parts by weight). Part) degree.
- the former / the latter (weight ratio) 99.9 / 0.1 to 20 / 80 (for example, 99.7 / 0.3 to 30/70) or so, for example, 99.5 / 0.5 to 40/60 (for example, 99.3 / 0.7 to 45 / 55), preferably 99/1 to 50/50 (eg, 98.5 / 1.5 to 55/45), more preferably 98/2 to 60/40 (eg, 97.5 /
- / 40 particularly about 97/3 to 60/40 (for example, 96.5 / 3.5 to 65/35), usually 99/1 to 60/40 (for example, 98/2 to 65).
- / 35 preferably 97/3 to 70/30, more preferably 96/4 It may be a 80/20).
- the electrically conductive composition excellent in electroconductivity and adhesiveness can be obtained efficiently.
- the conductive composition of the present invention may further contain a solvent (or a dispersion medium).
- a composition containing such a solvent is suitable as a coating composition (coating conductive composition).
- the solvent is not particularly limited.
- alcohols ⁇ eg, aliphatic alcohols [eg, methanol, ethanol, propanol, isopropanol, butanol, hexanol, heptanol, octanol (1-octanol, 2-octanol, etc.)]
- Decanol lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1-hexanol, octadecyl alcohol, hexadecenol, oleyl alcohol and the like saturated or unsaturated C 1-30 aliphatic alcohols, preferably saturated or unsaturated C 8 -24 and aliphatic alcohols, alicyclic alcohols [e.g., cycloalkanols such as cyclohexanol; terpineol, terpene alcohols such as dihydro terpineol (e.g., Mo Terpene
- aliphatic alcohols eg, alkanols such as ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, 2-ethyl-1-hexanol, octanol, decanol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol
- Poly alkanediols such as 1,4-butanediol; glycerin and the like
- alicyclic alcohols eg cycloalkanols such as cyclohexanol; terpene alcohols such as terpineol and dihydroterpineol
- glycol ethers eg Cellosolves (C 1-4 alkyl cellosolve such as methyl cellosolve, ethyl cellosolve and butyl cellosolve
- carbitols methylcarbi Tol, ethyl carbitol
- the conductive composition of the present invention is a conventional additive, for example, a colorant (such as a dye / pigment), a hue improver, a dye fixing agent, a gloss, and the like within a range that does not impair the effects of the present invention.
- a colorant such as a dye / pigment
- a hue improver such as a dye fixing agent
- a gloss such as a gloss, and the like
- the conductive composition of the present invention may be a conductive composition containing a solvent as described above.
- the solid content concentration can be selected from a range of about 10% by weight or more (for example, 20 to 99% by weight), depending on the application. 20% by weight or more (eg, 30 to 98% by weight), preferably 40% by weight or more (eg, 50 to 97% by weight), more preferably 60% by weight or more (eg, 70 to 95% by weight), usually 50% It may be ⁇ 90% by weight (for example, 60 ⁇ 80% by weight).
- the viscosity of the conductive composition of the present invention is not particularly limited and can be appropriately selected depending on the application. For example, at 25 ° C., 1 to 300 Pa ⁇ s (for example, 3 to 200 Pa ⁇ s), preferably 5 to 150 Pa ⁇ s (for example, 7 to 100 Pa ⁇ s), more preferably about 10 to 100 Pa ⁇ s. If the viscosity is too small, there is a risk of dripping during application (for example, dispensing application), and if the viscosity is too large, stringing may occur. The viscosity is measured, for example, under the following conditions. Measuring equipment: Rheometer Measuring conditions: Shear strength 5 (1 / s), diameter 4 cm, 2 ° cone
- the conductive composition of the present invention is not particularly limited, and can be obtained by mixing each component.
- the conductive metal powder and the resin component containing metal nanoparticles may be obtained by dispersing in a solvent (or dispersion medium).
- the conductive composition (or conductive paste) of the present invention is useful for forming various molded products (conductive molded products) that require electrical conductivity (or conductive sites).
- the conductive composition of the present invention since it has conductivity, it can be used as a composition for forming wirings and circuits (or electrodes) on a substrate.
- the conductive composition of the present invention is suitable as a conductive adhesive because it can achieve high conductivity and thermal conductivity and is excellent in adhesion or adhesion to a substrate.
- the electroconductive molded object of this invention has at least the electroconductive site
- the conductive molded body can be used as a wiring or a circuit (or an electrode) in a wiring or circuit application by using a conductive portion formed of a conductive composition on a substrate.
- the conductive adhesive application the conductive molded body is a joining base composed of two base materials and a conductive adhesive that is interposed between the base materials and adheres (directly bonds) the two base materials.
- the conductive adhesive is formed of a conductive composition.
- the conductive composition forming the conductive portion is not particularly limited as long as it is a conductive composition containing metal flakes, metal nanoparticles, and a resin component, and the conductive composition of the present invention.
- the composition does not need to be the same as that of the composition, and for example, a resin component having no aromatic amine skeleton (for example, a thermosetting resin component such as an epoxy resin component) may be used as the resin component.
- a resin component having no aromatic amine skeleton for example, a thermosetting resin component such as an epoxy resin component
- the resin component is also the same resin component as described above (that is, a resin component having an aromatic amine skeleton).
- the metal flake may be a metal flake having a crystal structure in which a metal (or metal crystal) is grown (or two-dimensionally) in the form of flakes (or crystal growth), and in particular, (111) in X-ray diffraction.
- the value X represented by the above formula is 25% or less (for example, 0 to 22%), preferably 20% or less.
- Metal flakes for example, 0 to 18%), more preferably 15% or less (for example, 0 to 12%), particularly preferably 10% or less (for example, 0 to 9%) may be used.
- the conductive composition forming the conductive site is the conductive composition of the present invention or not, the diffraction integration of the (111) plane and (200) plane in the X-ray diffraction of the conductive site.
- the intensities are I 111 and I 200 , respectively, the value X represented by the above formula is 25% or less (for example, 0 to 22%), preferably 20% or less (for example, 0 to 18%), More preferably, it is 15% or less (for example, 0 to 12%), and particularly preferably 10% or less (for example, 0 to 9%).
- Such a molded body can be obtained by applying (or coating) a conductive composition on a base material and curing it.
- a conductive composition is normally apply
- the substrate (or substrate) is not particularly limited and can be appropriately selected depending on the application.
- the material constituting the substrate may be an inorganic material (inorganic material) or an organic material (organic material).
- inorganic materials include glasses (soda glass, borosilicate glass, crown glass, barium-containing glass, strontium-containing glass, boron-containing glass, low alkali glass, alkali-free glass, crystallized transparent glass, silica glass, and quartz glass.
- Ceramics ⁇ metal oxide (silicon oxide, quartz, alumina or aluminum oxide, zirconia, sapphire, ferrite, titania or titanium oxide, zinc oxide, niobium oxide, mullite, beryllia, etc.), metal nitride (nitriding) Aluminum, silicon nitride, boron nitride, carbon nitride, titanium nitride, etc.), metal carbide (silicon carbide, boron carbide, titanium carbide, tungsten carbide, etc.), metal boride (titanium boride, zirconium boride, etc.), metal double oxidation Product [metal titanate ( Barium titanate, strontium titanate, lead titanate, niobium titanate, calcium titanate, magnesium titanate, etc.), metal zirconate (barium zirconate, calcium zirconate, lead zirconate, etc.) etc.], etc., metal (Aluminum, copper, gold,
- organic material examples include polymethyl methacrylate resin, styrene resin, vinyl chloride resin, polyester resin [polyalkylene arylate resin (polyalkylene arylate resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. Etc.), polyamide resins, polycarbonate resins, polysulfone resins, polyethersulfone resins, polyimide resins, cellulose derivatives, fluororesins, and the like.
- polyester resin polyalkylene arylate resin (polyalkylene arylate resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. Etc.), polyamide resins, polycarbonate resins, polysulfone resins, polyethersulfone resins, polyimide resins, cellulose derivatives, fluororesins, and the like.
- materials having high heat resistance such as inorganic materials such as semiconductors, glasses and metals, engineering plastics [for example, aromatic polyester resins (polyalkylene arylate resins such as polyethylene naphthalate, polyarylate resins) Etc.), polyimide resins, polysulfone resins, etc.], liquid crystal polymers, plastics such as fluororesins are preferred.
- the two substrates may be the same or different substrates.
- Specific examples of the combination of base materials can be appropriately selected according to the application, and are a combination of a base material formed of metal and a base material formed of metal, formed of a base material formed of metal and a semiconductor The combination with the made base material etc. are mentioned.
- the metal When used as an adhesive between metals, the metal may be formed on a non-metallic base material (for example, semiconductor, plastic, etc.) as long as the metal and the metal can be bonded.
- a non-metallic base material for example, semiconductor, plastic, etc.
- one base is a lead frame [for example, a lead frame formed of metal (copper, copper alloy, etc.)], and the other base is a semiconductor substrate.
- a semiconductor chip for example, a semiconductor substrate (such as a silicon substrate), a combination of a semiconductor chip or the like in which a metal film (such as titanium, platinum, or gold) is formed on a semiconductor substrate (such as a silicon substrate)
- a semiconductor substrate such as a silicon substrate
- a metal film such as titanium, platinum, or gold
- the surface of the base material is subjected to oxidation treatment [surface oxidation treatment such as discharge treatment (corona discharge treatment, glow discharge, etc.), acid treatment (chromic acid treatment, etc.), ultraviolet irradiation treatment, wrinkle treatment, etc., surface unevenness treatment (solvent Surface treatment such as treatment, sandblast treatment, etc.).
- surface oxidation treatment such as discharge treatment (corona discharge treatment, glow discharge, etc.), acid treatment (chromic acid treatment, etc.), ultraviolet irradiation treatment, wrinkle treatment, etc., surface unevenness treatment (solvent Surface treatment such as treatment, sandblast treatment, etc.).
- the thickness of the substrate may be appropriately selected depending on the application, and may be, for example, about 0.001 to 10 mm, preferably 0.01 to 5 mm, and more preferably about 0.05 to 3 mm.
- Examples of the coating method of the conductive composition on the substrate include, for example, a flow coating method, a spin coating method, a spray coating method, a screen printing method, a flexographic printing method, a casting method, a bar coating method, a curtain coating method, and a roll coating. Method, gravure coating method, dipping method, slit method, photolithography method, inkjet method and the like.
- the conductive composition may be formed in part or in whole with respect to the entire surface of the substrate depending on the application. For example, when forming a wiring or a circuit, a coating film of the conductive composition may be formed in a pattern, and when used as a conductive adhesive, the shape of the adherend between two substrates is used. You may form the coating film of an electroconductive composition according to these.
- a coating film in a pattern for example, screen printing, ink jet printing, intaglio printing (eg, gravure printing), offset printing, intaglio offset printing, flexographic printing, etc. It may be used for coating.
- the heating temperature can be selected according to the type of solvent, and is, for example, about 50 to 200 ° C., preferably about 80 to 180 ° C., and more preferably about 100 to 150 ° C. (particularly 110 to 140 ° C.).
- the heating time is, for example, about 1 minute to 3 hours, preferably about 5 minutes to 2 hours, and more preferably about 10 minutes to 1 hour.
- the applied film (coating film) is in an uncured (precursor) conductive composition and is usually subjected to a curing treatment.
- the curing treatment can usually be performed by at least heating (or baking or heat treatment).
- the heating temperature may be, for example, about 100 to 350 ° C., preferably 120 to 320 ° C., more preferably about 150 to 300 ° C. (for example, 180 to 250 ° C.).
- the heating time may be, for example, about 10 minutes to 5 hours, preferably 15 minutes to 3 hours, more preferably about 20 minutes to 1 hour, depending on the heating temperature.
- the thickness of the obtained conductive part or conductive film can be appropriately selected from the range of about 0.01 to 10,000 ⁇ m depending on the application, for example, 0.01 to 100 ⁇ m, Preferably, it may be about 0.1 to 50 ⁇ m, more preferably about 0.3 to 30 ⁇ m (particularly 0.5 to 10 ⁇ m).
- a relatively thick film for example, 0.3 ⁇ m or more (for example, 0.3 to 100 ⁇ m), preferably 0.5 ⁇ m or more (for example, 0.5 to 50 ⁇ m), more preferably 1 ⁇ m or more (for example, 1 to 1 ⁇ m).
- a metal film having a thickness of about 30 ⁇ m may be formed. Even if it is such a thick film, it can be set as a highly electroconductive metal film, without impairing the adhesiveness with respect to a base material.
- Aromatic amine resin component A To 3.75 parts by weight of bisphenol A propoxy diglycidyl ether (manufactured by Wako Pure Chemical Industries, epoxy equivalent 228 g / eq), aromatic polyamine [manufactured by Tokyo Chemical Industry, 4,4′-methylenebis (2-ethyl-6-methylaniline) )] 1.25 parts by weight were mixed to prepare an aromatic amine resin component A.
- Aromaatic amine resin component B 1.27 parts by weight of an aromatic polyamine (Wako Pure Chemicals, 4,4′-diaminodiphenyl ether) is added to 3.73 parts by weight of bisphenol A propoxydiglycidyl ether (Wako Pure Chemicals, epoxy equivalent 228 g / eq). By mixing, an aromatic amine resin component B was produced.
- Aromaatic amine resin component D An aromatic polyamine [manufactured by Tokyo Chemical Industry Co., Ltd., 4,4′-methylenebis (2-ethyl-6-) is added to 3.56 parts by weight of a phenol novolac type epoxy resin (Mitsubishi Chemical, “jER152”, epoxy equivalent 174 g / eq). Methylaniline)] 1.44 parts by weight were mixed to prepare an aromatic amine resin component D.
- (Aromatic amine resin component E) Block isocyanate (manufactured by Asahi Kasei Chemicals, “Duranate SBN-70D”, polyisocyanate obtained by blocking 1,6-hexamethylene diisocyanate with a pyrazole derivative, resin content 70% by weight, NCO rate 10.10%) 5.75 parts by weight ( 0.98 parts by weight of an aromatic polyamine [manufactured by Tokyo Chemical Industry Co., Ltd., 4,4′-methylenebis (2-ethyl-6-methylaniline)] is mixed with 4.02 parts by weight of the resin. Component E was made.
- Non-aromatic amine resin component A Bisphenol A propoxy diglycidyl ether (manufactured by Wako Pure Chemical Industries, epoxy equivalent: 228 g / eq) 4.75 parts by weight is mixed with dicyandiamide (Mitsubishi Chemical, "DICY-7") 0.25 parts by weight, non-aromatic A group amine resin component A was prepared.
- Non-aromatic amine resin component B 6.58 parts by weight of blocked isocyanate (manufactured by Asahi Kasei Chemicals, “Duranate SBN-70D”, polyisocyanate obtained by blocking 1,6-hexamethylene diisocyanate with a pyrazole derivative, resin content 70 wt%, NCO ratio 10.10%)
- Non-aromatic amine resin component B was prepared by mixing 0.39 parts by weight of an aliphatic polyamine (manufactured by Tokyo Chemical Industry Co., Ltd., triethylenetetramine) with respect to the resin content (4.61 parts by weight).
- Silver flake A was produced according to Example 2 of Japanese Patent No. 4144856.
- Silver flake B Silver flakes B were produced according to Example 2 of Japanese Patent No. 4399799.
- Silver flake C Commercially available silver flakes ("Q03R flake 2", manufactured by Mitsui Mining & Smelting Co., Ltd.) obtained by flattening a spherical silver powder produced by liquid phase reduction of a silver salt with a ball mill.
- Silver nanoparticles a Commercially available silver nanoparticles (Mitsuboshi Belting, “MDot-SLP”, spherical silver powder produced by liquid phase reduction of silver salt) were used.
- the average particle size (D50) of the silver nanoparticles a as measured by transmission electron microscope was 63 nm, and the particle size distribution was 1 to 200 nm.
- Silver nanoparticles b Commercially available silver nanoparticles (“Mitsui Metal Mining Co., Ltd.,“ EHD ”, spherical silver powder produced by liquid phase reduction of silver salt) were used.
- the average particle diameter (D50) of the silver nanoparticles b as measured by a scanning electron microscope was 650 nm, and the particle size distribution was 380 to 800 nm.
- the collected precipitate was redispersed in 2.2.4-trimethylpentane, filtered and dried to obtain silver nanoparticles c.
- the silver contains 75% by weight of silver and the remaining 25% by weight is a protective colloid component.
- the average particle diameter (D50) of the silver nanoparticles c measured with a transmission electron microscope was 5 nm, and the particle size distribution was 1 to 10 nm.
- the average particle diameter (D50) of the silver flakes is a volume-based center particle diameter measured using a laser diffraction / scattering particle size distribution measuring device (manufactured by Nikkiso, “Microtrack”).
- the average particle diameter (D50) of the silver nanoparticles is a volume-based center particle diameter measured using a transmission electron microscope. Note that the volume was converted on the assumption that the particles were spherical.
- the push ring was attached to a position about 2 mm lower than the sample surface of the sample holder, and silver flake powder was put therein. After the sample surface was brought into close contact with the glass plate, the pressing ring was pushed with a pushing jig from the opposite side, the silver flake powder was hardened so that the sample surface was flat, and a measurement sample was prepared.
- X-ray diffractometer RINTKU, RINT1200
- measuring conditions are 2 ⁇ / ⁇ scan method
- scanning angle is 35-55 °
- the integrated intensity values of diffraction peaks from the (111) plane of about 38 ° and the (200) plane of about 44 ° are I 111 and I 200 , respectively, and [I 200 / (I 111 + I 200 )] ⁇ 100 (%) was calculated.
- the crystallinity of the conductive composition was measured as follows.
- the conductive composition was applied onto a polytetrafluoroethylene (PTFE) plate with an applicator, and heated at 120 ° C. for 30 minutes and then at 200 ° C. for 90 minutes to produce a film-like cured product having a thickness of about 200 to 400 ⁇ m. .
- the film-like cured product was peeled off from the polytetrafluoroethylene plate, and XRD measurement was performed on the surface coated with the applicator (surface side) and the surface in contact with the PTFE plate (PTFE side). The measurement was performed under the same conditions as when silver flakes were measured.
- the conductive composition is applied onto a slide glass using an applicator, dried at 120 ° C. for 30 minutes, and then dried and fired under predetermined conditions (in Example 6 and Reference Example 4, it is fired at 120 ° C. for 30 minutes without drying) Otherwise, after drying at 120 ° C. for 30 minutes and firing at 200 ° C. for 90 minutes), a conductive film having a thickness of 15 ⁇ m is formed. Was calculated.
- the conductive composition is applied to a slide glass (substrate) using an applicator, dried at 120 ° C. for 30 minutes, and then dried and fired under predetermined conditions (in Example 6 and Reference Example 4, at 120 ° C. without drying).
- a conductive film having a thickness of 15 ⁇ m was formed by baking for 30 minutes, otherwise drying at 120 ° C. for 30 minutes, and baking at 200 ° C. for 90 minutes.
- a cellophane tape with a width of 24 mm (manufactured by Nichiban Co., Ltd.) is attached to the conductive film formed on the glass substrate, and after applying a load of about 5 kg, the load is rubbed so that bubbles between the conductive film and the cellophane tape disappear. By removing the bubbles, the cellophane tape and the substrate were brought into close contact with each other. Then, fix the substrate, lift the cellophane tape, peel it off at a speed of about 0.6 seconds, taking care that the angle between the substrate and the tape is about 90 degrees, and the peeling of the conductive film will adhere to the tape at all. When it was not, it was determined that the adhesion was good (A), and when part or all of the conductive film was peeled, it was determined that the adhesion was not good (B).
- a 3.5 mm ⁇ 3.5 mm silicon chip was attached to a copper plate having a thickness of 2 mm, dried at 120 ° C. for 30 minutes, and then baked at 200 ° C. for 90 minutes.
- the silicon chip (bonded surface is gold) provided with a film formed by sputtering in the order of titanium, platinum, and gold] was bonded to the copper plate, and then evaluated by measuring the shear strength.
- the thickness of the adhesive layer after curing was 30 ⁇ m, and the number of measurement samples was 4.
- Example 1 Three parts of 50 parts by weight of silver flake A, 50 parts by weight of silver nanoparticles a, 5 parts by weight of aromatic amine resin component A, and 10 parts by weight of triethylene glycol monobutyl ether (manufactured by Wako Pure Chemical Industries) as a solvent. The mixture was kneaded to obtain a conductive composition. And various characteristics were evaluated about the obtained electroconductive composition.
- Example 2 In Example 1, the conductive composition was the same as Example 1 except that 75 parts by weight of silver flake A was used instead of 50 parts by weight, and 25 parts by weight of silver nanoparticles a was used instead of 50 parts by weight. Got. And various characteristics were evaluated about the obtained electroconductive composition.
- Example 4 In Example 1, it replaced with 5 weight part aromatic amine resin component A, and obtained the electrically conductive composition like Example 1 except having used 5 weight part aromatic amine resin component C. . And various characteristics were evaluated about the obtained electroconductive composition.
- Example 5 In Example 1, it replaced with 5 weight part aromatic amine resin component A, and obtained the electrically conductive composition like Example 1 except having used 5 weight part aromatic amine resin component D. . And various characteristics were evaluated about the obtained electroconductive composition.
- Example 6 In Example 1, in place of 5 parts by weight of the aromatic amine resin component A, 6.73 parts by weight (5 parts by weight of the resin component) of the aromatic amine resin component E is used, and 10 parts by weight of triethylene glycol monoester is used. A conductive composition was obtained in the same manner as in Example 1 except that 9 parts by weight of diethylene glycol monobutyl ether (manufactured by Wako Pure Chemical Industries) was used instead of butyl ether. And various characteristics were evaluated about the obtained electroconductive composition.
- diethylene glycol monobutyl ether manufactured by Wako Pure Chemical Industries
- Example 7 In Example 1, it replaced with 50 weight part silver flake A, and except having used 50 weight part silver flake B, it carried out similarly to Example 1, and obtained the electroconductive composition. And various characteristics were evaluated about the obtained electroconductive composition.
- Example 8 In Example 1, it replaced with 50 weight part silver flake A, and except having used 50 weight part silver flake C, it carried out similarly to Example 1, and obtained the electroconductive composition. And various characteristics were evaluated about the obtained electroconductive composition.
- Example 9 In Example 1, it replaced with 50 weight part silver nanoparticles a, and except having used 50 weight part silver nanoparticles b, it carried out similarly to Example 1, and obtained the conductive composition. And various characteristics were evaluated about the obtained electroconductive composition.
- Example 10 95 parts by weight of silver flake A, 6.67 parts by weight of silver nanoparticles c (5 parts by weight as silver), 5 parts by weight of aromatic amine resin component A, and the silver concentration in the paste is 80% by weight Then, terpineol (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent was added and kneaded with three rolls to obtain a conductive composition. And various characteristics were evaluated about the obtained electroconductive composition.
- terpineol manufactured by Wako Pure Chemical Industries, Ltd.
- Example 11 90 parts by weight of silver flake A, 13.33 parts by weight of silver nanoparticles c (10 parts by weight as silver), 5 parts by weight of aromatic amine resin component A, and the silver concentration in the paste is 80% by weight Terpineol (manufactured by Wako Pure Chemical Industries) as a solvent was added and kneaded with three rolls to obtain a conductive composition. And various characteristics were evaluated about the obtained electroconductive composition.
- Example 12 In Example 1, the electrically conductive composition was obtained like Example 1 except having used 10 weight part of aromatic amine resin component A instead of 5 weight part. And various characteristics were evaluated about the obtained electroconductive composition.
- Example 13 In Example 10, the electrically conductive composition was obtained like Example 10 except having used 10 weight part of aromatic amine resin component A instead of 5 weight part. And various characteristics were evaluated about the obtained electroconductive composition.
- Example 1 the conductive composition was prepared in the same manner as in Example 1 except that silver flake A was not used and 100 parts by weight of silver nanoparticles a was used instead of 50 parts by weight of silver nanoparticles a. Obtained. And various characteristics were evaluated about the obtained electroconductive composition.
- Example 2 silver flake A was not used, but instead of 50 parts by weight of silver nanoparticles a, 50 parts by weight of silver nanoparticles a and 50 parts by weight of silver nanoparticles b were used. In the same manner, a conductive composition was obtained. And various characteristics were evaluated about the obtained electroconductive composition.
- Example 3 a conductive composition was obtained in the same manner as in Example 1 except that 5 parts by weight of the non-aromatic amine resin component A was used instead of 5 parts by weight of the aromatic amine resin component A. . And various characteristics were evaluated about the obtained electroconductive composition.
- Example 4 In Example 1, 6.97 parts by weight (5 parts by weight of resin component) of non-aromatic amine resin component B was used in place of 5 parts by weight of aromatic amine resin component A, and 10 parts by weight of triethylene glycol monoester was used. A conductive composition was obtained in the same manner as in Example 1 except that 10 parts by weight of diethylene glycol monobutyl ether (manufactured by Wako Pure Chemical Industries) was used instead of butyl ether. And various characteristics were evaluated about the obtained electroconductive composition.
- diethylene glycol monobutyl ether manufactured by Wako Pure Chemical Industries
- the conductive composition of the present invention can realize high conductivity, it can be used as a composition for forming various applications such as wiring, circuits, electrodes, and conductive adhesives.
- high conductivity and heat dissipation can be realized without impairing high adhesion, it is suitable as a conductive adhesive for bonding two substrates.
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Abstract
Description
本発明の導電性組成物は、特定の導電性金属粉および特定の樹脂成分で構成されている。
導電性金属粉は、金属フレーク(フレーク状金属粉、板状金属粉、鱗片状金属粉)と金属ナノ粒子とを少なくとも含んでいる。
金属フレークを構成する金属(金属原子)としては、例えば、遷移金属(例えば、チタン、ジルコニウムなどの周期表第4族金属;バナジウム、ニオブなどの周期表第5族金属;モリブデン、タングステンなどの周期表第6族金属;マンガン、レニウムなどの周期表第7族金属;鉄、ニッケル、コバルト、ルテニウム、ロジウム、パラジウム、イリジウム、白金などの周期表第8~10族金属;銅、銀、金などの周期表第11族金属など)、周期表第12族金属(例えば、亜鉛、カドミウムなど)、周期表第13族金属(例えば、アルミニウム、ガリウム、インジウムなど)、周期表第14族金属(例えば、ゲルマニウム、スズ、鉛など)、周期表第15族金属(例えば、アンチモン、ビスマスなど)などが挙げられる。金属は、単独で又は2種以上組み合わせてもよい。
金属フレークは、金属ナノ粒子と組み合わせて用いられる。金属フレークをこのような金属ナノ粒子と(さらには特定の樹脂成分と)組み合わせることで、効率よく高い導電性や密着性を実現できる。このような理由は定かではないが、金属フレーク間に金属ナノ粒子が介在することで、物理的に金属フレーク間の接触面積が増大したり、金属ナノ粒子の焼結により金属結合が形成されることもその一因であるものと考えられる。特に、このような効果は、金属界面における接触を補うという特徴を有するため、前記のような単結晶構造の金属フレークとの組み合わせにおいて、顕著である場合が多い。ただし、単純に金属フレークと金属ナノ粒子とを組み合わせても、十分な接触が担保できない場合があり、後述の特定の樹脂成分をさらに組み合わせることで、高い導電性を実現できる。
本発明において、導電性組成物を構成する樹脂成分は、芳香族アミン骨格(又は芳香族アミン由来の骨格)を有する。金属フレークに対して、金属ナノ粒子と芳香族アミン骨格を有する樹脂成分とを組み合わせることにより、高い導電性を実現でき、基板に対する十分な密着性を担保できる。このような理由は定かではないが、芳香族アミン骨格を有する樹脂が、何らかの形で金属フレーク同士、金属フレークと金属ナノ粒子、さらには金属ナノ粒子同士の接触や焼結(金属結合の形成)を促進する場合がある他、剛直な芳香族アミン骨格を有する樹脂構造と、金属フレークおよび金属ナノ粒子との組み合わせにおいて形成される剛直なメタルネットワーク構造との相性の良さも想定される。
代表的なエポキシ樹脂成分としては、エポキシ樹脂と芳香族アミン系硬化剤で構成された硬化剤とを含むエポキシ樹脂成分が含まれる。
代表的なポリイソシアネート樹脂成分としては、ポリイソシアネート化合物と芳香族アミン系硬化剤で構成された硬化剤とを含むポリイソシアネート樹脂成分が含まれる。
本発明の導電性組成物は、溶媒(又は分散媒)をさらに含んでいてもよい。このような溶媒を含む組成物(特にペースト状組成物)は、コーティング用組成物(コーティング用導電性組成物)として好適である。溶媒としては、特に限定されず、例えば、水、アルコール類{例えば、脂肪族アルコール類[例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ヘキサノール、ヘプタノール、オクタノール(1-オクタノール、2-オクタノールなど)、デカノール、ラウリルアルコール、テトラデシルアルコール、セチルアルコール、2-エチル-1-ヘキサノール、オクタデシルアルコール、ヘキサデセノール、オレイルアルコールなどの飽和又は不飽和C1-30脂肪族アルコール、好ましくは飽和又は不飽和C8-24脂肪族アルコールなど]、脂環族アルコール類[例えば、シクロヘキサノールなどのシクロアルカノール類;テルピネオール、ジヒドロテルピネオールなどのテルペンアルコール類(例えば、モノテルペンアルコールなど)など]、芳香脂肪族アルコール(例えば、ベンジルアルコール、フェネチルアルコールなど)、多価アルコール類(エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、ポリエチレングリコールなどの(ポリ)C2-4アルキレングリコールなどのグリコール類;グリセリンなどの3以上のヒドロキシル基を有する多価アルコールなど)など}、グリコールエーテル類(例えば、エチレングリコールモノメチルエーテル(メチルセロソルブ)、エチレングリコールモノエチルエーテル(エチルセロソルブ)、エチレングリコールモノブチルエーテル(ブチルセロソルブ)、ジエチレングリコールモノメチルエーテル(メチルカルビトール)、ジエチレングリコールモノエチルエーテル(エチルカルビトール)、ジエチレングリコールモノブチルエーテル(ブチルカルビトール)、トリエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールブチルエーテルなどの(ポリ)アルキレングリコールモノアルキルエーテル;2-フェノキシエタノールなどの(ポリ)アルキレングリコールモノアリールエーテルなど)、グリコールエステル類(例えば、酢酸カルビトールなどの(ポリ)アルキレングリコールアセテートなど)、グリコールエーテルエステル類(例えば、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテートなどの(ポリ)アルキレングリコールモノアルキルエーテルアセテート)、炭化水素類[例えば、脂肪族炭化水素類(例えば、ヘキサン、トリメチルペンタン、オクタン、デカン、ドデカン、テトラデカン、オクタデカン、ヘプタメチルノナン、テトラメチルペンタデカンなどの飽和又は不飽和脂肪族炭化水素類)、脂環式炭化水素類(シクロヘキサンなど)、ハロゲン化炭化水素類(塩化メチレン、クロロホルム、ジクロロエタンなど)、芳香族炭化水素類(例えば、トルエン、キシレンなど)など]、エステル類(例えば、酢酸メチル、酢酸エチル、酢酸ベンジル、酢酸イソボルネオール、安息香酸メチル、安息香酸エチルなど)、アミド類(ホルムアミド、アセトアミド、N-メチルホルムアミド、N-メチルアセトアミド,N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミドなどのモノ又はジC1-4アシルアミド類など)、ケトン類(アセトン、メチルエチルケトン、メチルイソブチルケトンなど)、エーテル類(ジエチルエーテル、ジプロピルエーテル、ジオキサン、テトラヒドロフランなど)、有機カルボン酸類(酢酸など)などが挙げられる。これらの溶媒は単独で又は2種以上組み合わせてもよい。
測定機器: レオメータ
測定条件: 剪断強度5(1/s)、径4cm、2°コーン
本発明の導電性組成物(又は導電性ペースト)は、導電性(又は導電性部位)を要する種々の成形体(導電性成形体)を形成するのに有用である。例えば、本発明の導電性組成物は、導電性を有しているため、基材上に配線や回路(又は電極)を形成するための組成物として利用できる。特に、本発明の導電性組成物は、高い導電性や熱伝導性を実現できるとともに、基材に対する密着性又は接着性に優れているため、導電性接着剤として好適である。
ビスフェノールAプロポキシジグリシジルエーテル(和光純薬製、エポキシ当量228g/eq)3.75重量部に対して、芳香族ポリアミン[東京化成製、4,4’-メチレンビス(2-エチル-6-メチルアニリン)]1.25重量部を混合し、芳香族アミン樹脂成分Aを作製した。
ビスフェノールAプロポキシジグリシジルエーテル(和光純薬製、エポキシ当量228g/eq)3.73重量部に対して、芳香族ポリアミン(和光純薬製、4,4’-ジアミノジフェニルエーテル)1.27重量部を混合し、芳香族アミン樹脂成分Bを作製した。
ダイマー酸のジグリシジルエステル(三菱化学製、「jER871」、エポキシ当量420g/eq)4.24重量部に対して、芳香族ポリアミン[東京化成製、4,4’-メチレンビス(2-エチル-6-メチルアニリン)]0.76重量部を混合し、芳香族アミン樹脂成分Cを作製した。
フェノールノボラック型エポキシ樹脂(三菱化学製、「jER152」、エポキシ当量174g/eq)3.56重量部に対して、芳香族ポリアミン[東京化成製、4,4’-メチレンビス(2-エチル-6-メチルアニリン)]1.44重量部を混合し、芳香族アミン樹脂成分Dを作製した。
ブロックイソシアネート(旭化成ケミカルズ製、「デュラネートSBN-70D」、1,6-ヘキサメチレンジイソシアネートをピラゾール誘導体でブロックしたポリイソシアネート、樹脂含有量70重量%、NCO率10.10%)5.75重量部(樹脂分4.02重量部)に対して、芳香族ポリアミン[東京化成製、4,4’-メチレンビス(2-エチル-6-メチルアニリン)]0.98重量部を混合し、芳香族アミン樹脂成分Eを作製した。
ビスフェノールAプロポキシジグリシジルエーテル(和光純薬製、エポキシ当量228g/eq)4.75重量部に対して、ジシアンジアミド(三菱化学製、「DICY-7」)0.25重量部を混合し、非芳香族アミン樹脂成分Aを作製した。
ブロックイソシアネート(旭化成ケミカルズ製、「デュラネートSBN-70D」、1,6-ヘキサメチレンジイソシアネートをピラゾール誘導体でブロックしたポリイソシアネート、樹脂含有量70重量%、NCO率10.10%)6.58重量部(樹脂分4.61重量部)に対して、脂肪族ポリアミン(東京化成製、トリエチレンテトラミン)0.39重量部を混合し、非芳香族アミン樹脂成分Bを作製した。
特許第4144856号公報の実施例2に準じて、銀フレークAを作製した。得られた銀フレークAの平均粒径(D50)は、6.2μmであり、X=[I200/(I111+I200)]×100の値(%)は、5.01%であった。
特許第4399799号公報の実施例2に準じて、銀フレークBを作製した。得られた銀フレークAの平均粒径(D50)は、2.2μmであり、X=[I200/(I111+I200)]×100の値(%)は、7.88%であった。
市販の銀フレーク(三井金属鉱業製、「Q03Rフレーク2」。銀塩を液相還元して作製した球状銀粉をボールミルで扁平化したもの)を用いた。銀フレークCの平均粒径(D50)は、1.1μmであり、X=[I200/(I111+I200)]×100の値(%)は、30.78%であった。
市販の銀ナノ粒子(三ツ星ベルト製、「MDot-SLP」、銀塩を液相還元して作製した球状銀粉)を用いた。銀ナノ粒子aの透過型電子顕微鏡測定による平均粒径(D50)は、63nmであり、粒径分布は1~200nmであった。
市販の銀ナノ粒子(三井金属鉱業製、「EHD」、銀塩を液相還元して作製した球状銀粉)を用いた。銀ナノ粒子bの走査型電子顕微鏡測定による平均粒径(D50)は、650nmであり、粒径分布は380~800nmであった。
2,2,4-トリメチルペンタン1.0Lに、硝酸銀2.5g、オクチルアミン4.9g、リノール酸2.0gを加え溶解させた。これに、撹拌しながら、水素化ホウ素ナトリウム0.03Mを含むプロパノール溶液1.0Lを滴下速度0.1L/時間の速度で滴下し、3時間撹拌した。得られた黒色の貴金属塩溶液をエバポレータにより濃縮し、2.0Lのメタノールを添加して、褐色の沈殿物としての球状粒子を生成させた後、吸引ろ過により該沈殿物を回収した。前記操作により得られた沈殿物を2.2.4-トリメチルペンタンに分散させ、再度2.0Lのメタノールを添加して、余剰保護コロイドを除去し、褐色の沈殿物を生成させる洗浄・回収工程を3回行ない、回収した沈殿物を2.2.4-トリメチルペンタンに再分散させ、ろ過し、乾燥させ、銀ナノ粒子cを得た。銀として75重量%の銀が含まれており、残り25重量%は保護コロイド成分である。銀ナノ粒子cの透過型電子顕微鏡測定による平均粒径(D50)は、5nmであり、粒径分布は1~10nmであった。
銀フレークの平均粒径(D50)は、レーザー回折散乱式粒度分布測定装置(日機装製、「マイクロトラック」)を用いて測定された体積基準中心粒径である。
銀フレークの結晶性は、以下のようにして測定した。
導電性組成物をスライドガラスにアプリケータを用いて塗布し、120℃、30分間乾燥後、所定の条件で乾燥・焼成(実施例6および参考例4では乾燥することなく120℃で30分間焼成、それ以外は120℃で30分乾燥後、200℃で90分間焼成)して厚み15μmの導電膜を形成し、四探針法による表面抵抗と触針式膜厚計による膜厚から比抵抗を算出した。
導電性組成物をスライドガラス(基板)にアプリケータを用いて塗布し、120℃、30分間乾燥後、所定の条件で乾燥・焼成(実施例6および参考例4では乾燥することなく120℃で30分間焼成、それ以外は120℃で30分乾燥後、200℃で90分間焼成)して厚み15μmの導電膜を形成した。
導電性組成物を用いて、厚み2mmの銅板に3.5mm×3.5mmのシリコンチップを貼り付け、120℃で30分間乾燥後、200℃で90分間焼成して、シリコンチップ[シリコン上に、チタン、白金、金の順にスパッタリングによる膜を設けたシリコンチップ(接着面は金)]を銅板と接着させた後、剪断強度を測定することで評価した。硬化後の接着層の厚みは30μm、測定サンプル数は4とした。
測定した比抵抗値を用い、ヴィーデマン・フランツ則による式 λ=L×T/ρv(λは熱伝導率、Lはローレンツ数(2.44×10―8W・Ω・K―2)、Tは絶対温度(298K)、ρvは比抵抗)を用いて、熱伝導率を測定した。
50重量部の銀フレークA、50重量部の銀ナノ粒子a、5重量部の芳香族アミン樹脂成分A、溶媒としてのトリエチレングリコールモノブチルエーテル(和光純薬製)10重量部を三本ロールで混練し、導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、銀フレークAを50重量部に代えて75重量部、銀ナノ粒子aを50重量部に代えて25重量部用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、5重量部の芳香族アミン樹脂成分Aに代えて、5重量部の芳香族アミン樹脂成分Bを用いるとともに、10重量部のトリエチレングリコールモノブチルエーテルに代えて10重量部のペンタンジオール/テルピネオール混合溶媒(重量比=1/2)を用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、5重量部の芳香族アミン樹脂成分Aに代えて、5重量部の芳香族アミン樹脂成分Cを用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、5重量部の芳香族アミン樹脂成分Aに代えて、5重量部の芳香族アミン樹脂成分Dを用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、5重量部の芳香族アミン樹脂成分Aに代えて、6.73重量部(樹脂成分5重量部)の芳香族アミン樹脂成分Eを用いるとともに、10重量部のトリエチレングリコールモノブチルエーテルに代えて9重量部のジエチレングリコールモノブチルエーテル(和光純薬製)を用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、50重量部の銀フレークAに代えて50重量部の銀フレークBを用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、50重量部の銀フレークAに代えて50重量部の銀フレークCを用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、50重量部の銀ナノ粒子aに代えて50重量部の銀ナノ粒子bを用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
95重量部の銀フレークA、6.67重量部の銀ナノ粒子c(銀として5重量部)、5重量部の芳香族アミン樹脂成分A、ペースト中の銀濃度が80重量%になるように、溶媒としてのテルピネオール(和光純薬製)を加え、三本ロールで混練し、導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
90重量部の銀フレークA、13.33重量部の銀ナノ粒子c(銀として10重量部)、5重量部の芳香族アミン樹脂成分A、ペースト中の銀濃度が80重量%になるように溶媒としてのテルピネオール(和光純薬製)を加え、三本ロールで混練し、導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、芳香族アミン樹脂成分Aを5重量部に代えて10重量部用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例10において、芳香族アミン樹脂成分Aを5重量部に代えて10重量部用いたこと以外は、実施例10と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、銀フレークAを用いず、50重量部の銀ナノ粒子aに代えて100重量部の銀ナノ粒子aを用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、銀フレークAを用いず、50重量部の銀ナノ粒子aに代えて50重量部の銀ナノ粒子aおよび50重量部の銀ナノ粒子bを用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、5重量部の芳香族アミン樹脂成分Aに代えて5重量部の非芳香族アミン樹脂成分Aを用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
実施例1において、5重量部の芳香族アミン樹脂成分Aに代えて6.97重量部(樹脂成分5重量部)の非芳香族アミン樹脂成分Bを用いるとともに、10重量部のトリエチレングリコールモノブチルエーテルに代えて10重量部のジエチレングリコールモノブチルエーテル(和光純薬製)を用いたこと以外は、実施例1と同様にして導電性組成物を得た。そして、得られた導電性組成物について、各種特性を評価した。
本出願は、2012年9月27日出願の日本特許出願2012-215008及び2012年11月16日出願の日本特許出願2012-252058に基づくものであり、その内容はここに参照として取り込まれる。
Claims (18)
- 導電性金属粉と樹脂成分とを含む組成物であって、導電性金属粉が金属フレークと金属ナノ粒子とを含み、樹脂成分が芳香族アミン骨格を含む導電性組成物。
- 金属フレークが、金属結晶がフレーク状に成長した結晶構造を有する請求項1記載の導電性組成物。
- 金属フレークが、X線回折における(111)面、(200)面の回折積分強度を、それぞれ、I111、I200とするとき、下記式で表される値Xが20%以下の金属フレークである請求項1又は2記載の導電性組成物。
X=[I200/(I111+I200)]×100(%) - 金属ナノ粒子の平均粒径が2~200nmである請求項1~3のいずれか一項に記載の導電性組成物。
- 金属フレークと金属ナノ粒子との割合が、前者/後者(重量比)=99/1~30/70である請求項1~4のいずれか一項に記載の導電性組成物。
- 樹脂成分が、熱硬化性樹脂成分である請求項1~5のいずれか一項に記載の導電性組成物。
- 樹脂成分が、熱硬化性樹脂および硬化剤で構成され、熱硬化性樹脂及び/又は硬化剤が芳香族アミン骨格を含む熱硬化性樹脂成分である請求項1~6のいずれか一項に記載の導電性組成物。
- 硬化剤が芳香族アミン系硬化剤で構成されている請求項7記載の導電性組成物。
- 樹脂成分が、エポキシ樹脂と芳香族アミン系硬化剤で構成された硬化剤とを含むエポキシ樹脂成分であるか、又はポリイソシアネート化合物と芳香族アミン系硬化剤で構成された硬化剤とを含むポリイソシアネート樹脂成分である請求項7又は8記載の導電性組成物。
- 樹脂成分が、エポキシ当量が600g/eq以下のエポキシ樹脂、および芳香族アミン系硬化剤で構成された硬化剤を含むエポキシ樹脂成分である請求項7~9のいずれか一項に記載の導電性組成物。
- 芳香族アミン系硬化剤が、芳香環に直接アミノ基が置換した構造を有する芳香族アミン系硬化剤である請求項8~10のいずれか一項に記載の導電性組成物。
- 導電性金属粉と樹脂成分との割合が、前者/後者(重量比)=99/1~50/50である請求項1~11のいずれか一項に記載の導電性組成物。
- 金属フレークと金属ナノ粒子との割合が、前者/後者(重量比)=97/3~35/65であり、導電性金属粉と樹脂成分との割合が、前者/後者(重量比)=97/3~70/30である請求項1~12のいずれか一項に記載の導電性組成物。
- 導電性接着剤である請求項1~13のいずれか一項に記載の導電性組成物。
- 金属基材と半導体基材とを接着させるための導電性接着剤である請求項1~14のいずれか一項に記載の導電性組成物。
- 請求項1~15のいずれか一項に記載の導電性組成物で形成された導電性部位を少なくとも有する導電性成形体。
- 2つの基材とこの基材間に介在し、2つの基材を接着させる導電性接着剤とで構成された接合基材を備えた成形体であって、導電性接着剤が請求項1~15のいずれか一項に記載の導電性組成物により形成された導電性部位である請求項16記載の成形体。
- 金属フレークと金属ナノ粒子と樹脂成分とを含む導電性組成物で形成された導電性部位を少なくとも有する導電性成形体であって、導電性部位のX線回折における(111)面、(200)面の回折積分強度を、それぞれ、I111、I200とするとき、下記式で表される値Xが20%以下である、導電性成形体。
X=[I200/(I111+I200)]×100(%)
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Also Published As
Publication number | Publication date |
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CN104685002A (zh) | 2015-06-03 |
KR102005542B1 (ko) | 2019-07-30 |
TW201413739A (zh) | 2014-04-01 |
TWI553665B (zh) | 2016-10-11 |
EP2902449A1 (en) | 2015-08-05 |
EP2902449A4 (en) | 2016-04-06 |
JP2014080559A (ja) | 2014-05-08 |
CN104685002B (zh) | 2018-09-07 |
KR20150064039A (ko) | 2015-06-10 |
JP5827203B2 (ja) | 2015-12-02 |
EP2902449B1 (en) | 2018-09-19 |
US20150252224A1 (en) | 2015-09-10 |
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