WO2017159694A1 - Particule contenant du métal, matériau de connexion, structure connectée et procédé de production de structure connectée - Google Patents

Particule contenant du métal, matériau de connexion, structure connectée et procédé de production de structure connectée Download PDF

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Publication number
WO2017159694A1
WO2017159694A1 PCT/JP2017/010251 JP2017010251W WO2017159694A1 WO 2017159694 A1 WO2017159694 A1 WO 2017159694A1 JP 2017010251 W JP2017010251 W JP 2017010251W WO 2017159694 A1 WO2017159694 A1 WO 2017159694A1
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Prior art keywords
metal
particles
protrusion
particle
protrusions
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PCT/JP2017/010251
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English (en)
Japanese (ja)
Inventor
昌男 笹平
悠人 土橋
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積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to KR1020217040390A priority Critical patent/KR20210154865A/ko
Priority to CN201780003651.8A priority patent/CN108140450B/zh
Priority to JP2017516171A priority patent/JP7131908B2/ja
Priority to KR1020187010189A priority patent/KR20180120667A/ko
Publication of WO2017159694A1 publication Critical patent/WO2017159694A1/fr

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors

Definitions

  • the present invention relates to a metal-containing particle comprising a base particle and a metal part disposed on the surface of the base particle, the metal part having a protrusion on the outer surface.
  • the present invention also relates to a connection material, a connection structure, and a method for manufacturing the connection structure using the metal-containing particles.
  • connection material containing metal particles may be used to form a connection part that connects two connection target members.
  • connection material for performing such connection is disclosed in, for example, Patent Document 1 below.
  • the connection material described in Patent Document 1 includes nano-sized composite silver particles, nano-sized silver particles, and a resin.
  • the composite silver particle is a particle in which an organic coating layer is formed around a silver nucleus that is an aggregate of silver atoms.
  • the organic coating layer comprises at least one alcohol molecule residue having 10 or 12 carbon atoms, an alcohol molecule derivative (wherein the alcohol molecule derivative is limited to carboxylic acid and / or aldehyde) and / or alcohol molecules. It is formed by the alcohol component.
  • Patent Document 2 discloses a connection material including nano-sized metal-containing particles and conductive particles.
  • Metal particles such as nano-sized silver particles are melt-bonded by heat treatment at the time of connection to form a bulk.
  • the melting point becomes high, so that there is a problem that the heating temperature becomes high.
  • a gap is generated between the nano-sized particles. As a result, connection reliability is lowered.
  • Patent Document 1 since the composite silver particles have an alcohol component on the surface, voids are likely to be generated in the connection portion due to the alcohol component. As a result, connection reliability is lowered.
  • the method includes a base particle and a metal part disposed on a surface of the base particle, the metal part having a plurality of protrusions on an outer surface, and the metal part
  • the tip of the protrusion is provided with metal-containing particles that can be melted at 400 ° C. or lower.
  • the metal portion has a plurality of convex portions on the outer surface, and the metal portion has the protrusions on the outer surface of the convex portion.
  • the ratio of the average height of the protrusions to the average height of the protrusions is 5 or more and 1000 or less.
  • the average diameter of the base portion of the convex portion is 3 nm or more and 5000 nm or less.
  • the surface area of the portion having the convex portion is 10% or more in the total surface area of 100% of the outer surface of the metal portion.
  • the shape of the convex portion is a needle shape or a partial shape of a sphere.
  • the average apex angle of the protrusion is 10 ° or more and 60 ° or less.
  • the average height of the protrusions is 3 nm or more and 5000 nm or less.
  • the average diameter of the base of the protrusion is 3 nm or more and 1000 nm or less.
  • the ratio of the average height of the protrusion to the average diameter of the base of the protrusion is 0.5 or more and 10 or less.
  • the shape of the protrusion is a needle shape or a partial shape of a sphere.
  • the material of the protrusion includes silver, copper, gold, palladium, tin, indium, or zinc.
  • the material of the metal part is not solder.
  • the material of the metal part is silver, copper, gold, palladium, tin, indium, zinc, nickel, cobalt, iron, tungsten, molybdenum, ruthenium, platinum, rhodium. , Iridium, phosphorus or boron.
  • the tip of the protrusion of the metal part is preferably meltable at 350 ° C. or lower, more preferably 300 ° C. or lower, and further preferably It can be melted at 250 ° C. or lower, particularly preferably 200 ° C. or lower.
  • the base material particle is a silicone particle.
  • connection material including the metal-containing particles described above and a resin.
  • the material of the connection portion is the metal-containing particles described above or a connection material including the metal-containing particles and a resin.
  • the metal-containing particles described above are arranged between the first connection target member and the second connection target member, or the connection includes the metal-containing particles and the resin. Arranging the material, heating the metal-containing particles, melting the tips of the protrusions of the metal part, solidifying after melting, and using the metal-containing particles or the connection material, the first connection target member And a step of forming a connection part connecting the second connection target member.
  • a method for manufacturing a connection structure is provided.
  • the metal-containing particle according to the present invention includes a base particle and a metal part disposed on the surface of the base particle, the metal part has a plurality of protrusions on the outer surface, Since the tip of the projection can be melted at 400 ° C. or lower, the tip of the projection of the metal part of the metal-containing particle is melted at a relatively low temperature, solidified after melting, and joined to other particles or other members. Connection reliability can be improved.
  • FIG. 1 is a cross-sectional view schematically showing metal-containing particles according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing metal-containing particles according to the second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing metal-containing particles according to the third embodiment of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing metal-containing particles according to the fourth embodiment of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing metal-containing particles according to the fifth embodiment of the present invention.
  • FIG. 6 is a cross-sectional view schematically showing metal-containing particles according to the sixth embodiment of the present invention.
  • FIG. 1 is a cross-sectional view schematically showing metal-containing particles according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing metal-containing particles according to the second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing
  • FIG. 7 is a cross-sectional view schematically showing metal-containing particles according to the seventh embodiment of the present invention.
  • FIG. 8 is a cross-sectional view schematically showing metal-containing particles according to the eighth embodiment of the present invention.
  • FIG. 9 is a cross-sectional view schematically showing a connection structure using metal-containing particles according to the first embodiment of the present invention.
  • FIG. 10 is a cross-sectional view schematically showing a modified example of the connection structure using the metal-containing particles according to the first embodiment of the present invention.
  • FIG. 11 is a diagram showing an image of the produced metal-containing particles.
  • FIG. 12 is a diagram showing an image of the produced metal-containing particles.
  • FIG. 13 is a diagram showing an image of the produced metal-containing particles.
  • FIG. 14 is a diagram showing an image of the produced metal-containing particles.
  • FIG. 15 is a diagram showing an image of particles that are solidified after melting the tips of the protrusions of the metal part of the manufactured metal-containing particles.
  • FIG. 16 is a diagram showing an image of particles that are solidified after melting the tips of the protrusions of the metal part of the manufactured metal-containing particles.
  • FIG. 17 is a diagram showing an image of particles that are solidified after melting the tips of the protrusions of the metal part of the manufactured metal-containing particles.
  • FIG. 18 is a diagram showing an image of particles that have been solidified after melting the tips of the protrusions of the metal part of the manufactured metal-containing particles.
  • 19A and 19B are a plan view and a cross-sectional view showing an example of a continuity test member.
  • 20A to 20C are diagrams schematically showing a state in which the electrical characteristics of the electronic circuit device are inspected by the continuity inspection member.
  • the metal-containing particle according to the present invention includes a base particle and a metal part.
  • the said metal part is arrange
  • the metal part has a plurality of protrusions on the outer surface.
  • the tips of the protrusions of the metal part can be melted at 400 ° C. or lower.
  • the tip of the protrusion of the metal part can be melted at a relatively low temperature. For this reason, the tips of the protrusions of the metal part in the metal-containing particles can be melted at a relatively low temperature, solidified after melting, and bonded to other particles or other members.
  • a plurality of metal-containing particles can be melt bonded.
  • the metal-containing particles can be melt bonded to the connection target member. Still further, the metal-containing particles can be melt bonded to the electrode.
  • the particle size of metal particles is reduced to a size of 100 nm or less and the number of constituent atoms is reduced, the surface area ratio to the volume of the particles increases rapidly, and the melting point or sintering temperature decreases significantly compared to the bulk state. It has been known.
  • the present inventors can lower the melting temperature of the tip of the protrusion of the metal part, as in the case of using nano-sized metal particles. I found.
  • the protrusion may have a tapered needle shape.
  • a plurality of small protrusions may be formed on the outer surface of the metal part in order to lower the melting temperature of the tip of the protrusion of the metal part.
  • the metal part in order to reduce the melting temperature of the tip of the protrusion of the metal part, has a plurality of protrusions (first protrusions) on the outer surface, and the metal It is preferable that the portion has the protrusion (second protrusion) on the outer surface of the convex portion.
  • the convex portion is preferably larger than the protrusion.
  • the presence of the protrusions larger than the protrusions further increases connection reliability.
  • the protrusion and the protrusion may be integrated, or the protrusion may be attached on the protrusion.
  • the protrusion may be composed of particles.
  • a protrusion portion where the protrusion is formed on the outer surface is referred to as a convex portion in distinction from the protrusion.
  • the tip of the convex part may not be meltable at 400 ° C. or lower.
  • the melting temperature can be lowered by reducing the tip diameter of the protrusion.
  • the material of the metal part can be selected. It is preferable to select the shape of the protrusion and the material of the metal part so that the melting temperature at the tip of the protrusion of the metal part is 400 ° C. or lower.
  • the melting temperature at the tip of the protrusion of the metal part is evaluated as follows.
  • the melting temperature at the tip of the protrusion of the metal part can be measured using a differential scanning calorimeter (“DSC-6300” manufactured by Yamato Scientific Co., Ltd.). The above measurement was performed using 15 g of metal-containing particles, with a temperature increase range of 30 ° C. to 500 ° C., a temperature increase rate of 5 ° C./min. , Nitrogen purge amount 5 ml / min.
  • the measurement conditions are as follows.
  • the tip of the protrusion of the metal part is melted at the melting temperature obtained by the above measurement.
  • 1 g of metal-containing particles is placed in a container and placed in an electric furnace.
  • the same temperature as the melting temperature obtained by the above measurement is set in an electric furnace and heated in a nitrogen atmosphere for 10 minutes. Thereafter, the heated metal-containing particles are taken out from the electric furnace, and the molten state (or solidified state after melting) of the tip of the protrusion is confirmed using a scanning electron microscope.
  • the shape of the protrusion is preferably a tapered needle shape.
  • the shape of the protrusion on the outer surface of the metal portion is different from the conventional shape, and a new effect is exhibited due to the needle shape having a tapered protrusion shape.
  • the metal-containing particles according to the present invention can be used to connect two connection target members because the tips of the protrusions of the metal part can be melt-bonded at a relatively low temperature.
  • a connection part that exhibits a strong connection can be formed, and connection reliability can be improved.
  • the metal-containing particles according to the present invention may be used for conductive connection. Furthermore, the metal-containing particles according to the present invention can also be used as a gap control material (spacer).
  • the average apex angle (a) of the plurality of protrusions is preferably 10 ° or more, more preferably 20 ° or more, preferably 60 ° or less, more preferably 45 ° or less. If the average (a) of the apex angles is equal to or greater than the above lower limit, the protrusions are not easily broken. When the average (a) of the apex angles is not more than the above upper limit, the melting temperature is further lowered. Note that the broken protrusion may increase the connection resistance between the electrodes at the time of conductive connection.
  • the average (a) of the apex angles of the protrusions can be obtained by averaging the apex angles of the protrusions included in one metal-containing particle.
  • the average height (b) of the plurality of protrusions is preferably 3 nm or more, more preferably 5 nm or more, still more preferably 50 nm or more, preferably 5000 nm or less, more preferably 1000 nm or less, still more preferably 800 nm or less. .
  • the melting temperature is further lowered.
  • the average height (b) of the protrusions is not more than the above upper limit, the protrusions are not easily broken.
  • the average height (b) of the protrusions is the average height of protrusions included in one metal-containing particle.
  • the height of the protrusion is on the line connecting the center of the metal-containing particle and the tip of the protrusion (broken line L1 shown in FIG. 1).
  • the height of the protrusion has no protrusion.
  • the distance from the imaginary line of the metal part (convex part) to the tip of the protrusion is assumed.
  • the protrusion may be an aggregate of a plurality of granular materials.
  • the protrusion may be formed of a plurality of particles constituting the protrusion.
  • the height of the protrusion is the height of the protrusion when the aggregate of a plurality of granular materials or continuous particles are viewed as a whole.
  • the heights of the protrusions 1Ba and 3Ba indicate the distance from the imaginary line of the metal part to the tip of the protrusion when it is assumed that there is no protrusion.
  • the average diameter (c) of the bases of the plurality of protrusions is preferably 3 nm or more, more preferably 5 nm or more, still more preferably 50 nm or more, preferably 1000 nm or less, more preferably 800 nm or less.
  • the average diameter (c) is equal to or more than the lower limit, the protrusions are not easily broken.
  • connection reliability is further enhanced.
  • the average diameter (c) of the base of the protrusion is an average of the diameter of the base of the protrusion included in one metal-containing particle.
  • the diameter of the base is the maximum diameter of each of the bases in the protrusion.
  • the ratio of the average height (b) of the plurality of protrusions to the average diameter (c) of the bases of the plurality of protrusions is preferably 0.5 or more. More preferably, it is 1.5 or more, preferably 10 or less, more preferably 5 or less. When the ratio (average height (b) / average diameter (c)) is not less than the lower limit, the connection reliability is further increased. When the ratio (average height (b) / average diameter (c)) is not more than the above upper limit, the protrusions are not easily broken.
  • the ratio (average diameter (d) / average diameter (c)) of the average diameter (d) at the center of the height of the plurality of protrusions to the average diameter (c) of the bases of the plurality of protrusions is preferably It is 1/5 or more, more preferably 1/4 or more, still more preferably 1/3 or more, preferably 4/5 or less, more preferably 3/4 or less, still more preferably 2/3 or less.
  • the ratio (average diameter (d) / average diameter (c)) is not less than the lower limit, the protrusions are not easily broken.
  • the ratio (average diameter (d) / average diameter (c)) is not more than the above upper limit, the connection reliability is further enhanced.
  • the average diameter (d) at the center position of the protrusion height is the average diameter at the center position of the protrusion height included in one metal-containing particle.
  • the diameter at the central position of the height of the protrusion is the maximum diameter of each central position of the height of the protrusion.
  • the shape of the plurality of protrusions is a needle shape or a partial shape of a sphere.
  • the acicular shape is preferably a pyramid shape, a conical shape, or a paraboloidal shape, more preferably a conical shape or a parabolic shape, and still more preferably a conical shape.
  • the shape of the protrusion may be a pyramid shape, a cone shape, or a paraboloid. In the present invention, a rotating paraboloid is also included in the tapered needle shape.
  • the paraboloidal protrusion is tapered from the base to the tip.
  • the number of protrusions on the outer surface of the metal part per one metal-containing particle is preferably 3 or more, more preferably 5 or more.
  • the upper limit of the number of protrusions is not particularly limited.
  • the upper limit of the number of protrusions can be appropriately selected in consideration of the particle diameter of the metal-containing particles. Note that the protrusions included in the metal-containing particles do not have to be tapered, and it is not necessary that all the protrusions included in the metal-containing particles have a tapered needle shape.
  • the ratio of the number of protrusions that are tapered in the number of protrusions contained per metal-containing particle is preferably 30% or more, more preferably 50% or more, and still more preferably 60% or more. Particularly preferred is 70% or more, and most preferred is 80% or more. As the ratio of the number of needle-like protrusions increases, the effect of the needle-like protrusions can be obtained more effectively.
  • the ratio (x) of the surface area of the portion with protrusions is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more, preferably 90 % Or less, more preferably 80% or less, and still more preferably 70% or less.
  • the ratio of the surface area of the portion having the needle-like protrusion is preferably 10% or more, more preferably 20% or more, out of 100% of the entire surface area of the outer surface of the metal part. More preferably, it is 30% or more, preferably 90% or less, more preferably 80% or less, and still more preferably 70% or less. As the ratio of the surface area of the portion having the needle-like protrusion is larger, the effect of the protrusion is more effectively obtained.
  • the average (A) of the apex angles of the plurality of convex portions is preferably 10 ° or more, more preferably 20 ° or more, preferably 60 ° or less, more preferably 45 ° or less. If the average (A) of the apex angles is equal to or greater than the lower limit, the convex portion is not easily broken. When the average (A) of the apex angles is not more than the above upper limit, the melting temperature is further lowered. In addition, the broken convex part may raise the connection resistance between electrodes at the time of conductive connection.
  • the average (A) of the apex angles of the convex portions can be obtained by averaging the apex angles of the convex portions included in one metal-containing particle.
  • the average height (B) of the plurality of convex portions is preferably 5 nm or more, more preferably 50 nm or more, preferably 5000 nm or less, more preferably 1000 nm or less, and still more preferably 800 nm or less.
  • the melting temperature is further lowered.
  • the average height (B) of the convex portions is equal to or less than the upper limit, the convex portions are not easily broken.
  • the average height (B) of the convex portions is the average height of the convex portions included in one metal-containing particle.
  • the height of the convex part is an imaginary line of the metal part on the line connecting the center of the metal-containing particle and the tip of the convex part (broken line L1 shown in FIG. 8) assuming no convex part (FIG. 8).
  • the distance from the broken line L2) (on the outer surface of the spherical metal-containing particle when it is assumed that there is no projection) to the tip of the projection is shown. That is, in FIG. 8, the distance from the intersection of the broken line L1 and the broken line L2 to the tip of the convex portion is shown.
  • the average diameter (C) of the base portions of the plurality of convex portions is preferably 3 nm or more, more preferably 5 nm or more, still more preferably 50 nm or more, preferably 5000 nm or less, more preferably 1000 nm or less, still more preferably 800 nm or less. It is. When the average diameter (C) is equal to or greater than the lower limit, the convex portion is not easily broken. When the average diameter (C) is not more than the upper limit, the connection reliability is further increased.
  • the average diameter (C) of the base of the convex part is an average of the diameters of the bases of the convex parts included in one metal-containing particle.
  • the diameter of the base is the maximum diameter of each of the bases in the convex part.
  • the portion is the base of the convex portion, and the distance between the ends of the imaginary line portion (the distance connecting the ends with a straight line) is the diameter of the base.
  • the ratio (average diameter (D) / average diameter (C)) of the average diameter (D) at the center position of the height of the plurality of convex portions to the average diameter (C) of the base portions of the plurality of convex portions is: Preferably it is 1/5 or more, More preferably, it is 1/4 or more, More preferably, it is 1/3 or more, Preferably it is 4/5 or less, More preferably, it is 3/4 or less, More preferably, it is 2/3 or less.
  • the ratio (average diameter (D) / average diameter (C)) is equal to or greater than the lower limit, the convex portion is not easily broken.
  • the ratio (average diameter (D) / average diameter (C)) is not more than the above upper limit, the connection reliability is further enhanced.
  • the average diameter (D) at the central position of the height of the convex portion is an average of the diameters at the central position of the height of the convex portion included in one metal-containing particle.
  • the diameter at the central position of the height of the convex portion is the maximum diameter of each central position of the height of the convex portion.
  • the shape of the plurality of convex portions is a needle shape or a partial shape of a sphere.
  • the acicular shape is preferably a pyramid shape, a conical shape, or a paraboloidal shape, more preferably a conical shape or a parabolic shape, and still more preferably a conical shape.
  • the shape of the convex portion may be a pyramid shape, a cone shape, or a paraboloid.
  • a rotating paraboloid is also included in the tapered needle shape.
  • the parabolic convex portion is tapered from the base to the tip.
  • the number of protrusions on the outer surface of the metal part per metal-containing particle is preferably 3 or more, more preferably 5 or more.
  • the upper limit of the number of the convex portions is not particularly limited. The upper limit of the number of convex portions can be appropriately selected in consideration of the particle diameter of the metal-containing particles.
  • grain does not need to be a tapering needle shape, and all the convex parts contained in the said metal containing particle
  • the ratio of the number of convex portions that are tapered in the number of convex portions included in one metal-containing particle is preferably 30% or more, more preferably 50% or more, and still more preferably 60%. Above, especially preferably 70% or more, most preferably 80% or more. As the ratio of the number of needle-like convex portions increases, the effect of the needle-like convex portions can be obtained more effectively.
  • the ratio (X) of the surface area of the part having the convex part is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more, preferably It is 90% or less, more preferably 80% or less, still more preferably 70% or less. As the ratio of the surface area of the portion having the convex portion is increased, the effect of the protrusion on the convex portion is more effectively obtained.
  • the ratio of the surface area of the portion having the needle-like convex portion is preferably 10% or more, more preferably 20% or more, out of the entire surface area of the outer surface of the metal portion Further, it is preferably 30% or more, preferably 90% or less, more preferably 80% or less, still more preferably 70% or less. As the ratio of the surface area of the portion having the needle-like convex portion is larger, the effect of the protrusion on the convex portion is more effectively obtained.
  • the ratio (average height (B) / average height (b)) of the average height (B) of the plurality of protrusions to the average height (b) of the plurality of protrusions is preferably 5 or more. Preferably it is 10 or more, preferably 1000 or less, more preferably 800 or less. When the ratio (average height (B) / average height (b)) is equal to or higher than the lower limit, the connection reliability is further increased. When the ratio (average height (B) / average height (b)) is not more than the above upper limit, the convex portion is not easily broken.
  • the metal part having a plurality of the protrusions is formed by a crystal orientation of a metal or an alloy.
  • the metal part is formed by the crystal orientation of the metal or alloy.
  • the compression elastic modulus (10% K value) when the metal-containing particles are compressed by 10% is preferably 100 N / mm 2 or more, more preferably 1000 N / mm 2 or more. preferably 25000N / mm 2 or less, more preferably 10000 N / mm 2 or less, and more preferably not more than 8000 N / mm 2.
  • the compression elastic modulus (10% K value) of the metal-containing particles can be measured as follows.
  • the metal-containing particles are compressed under the conditions of a cylindrical indenter (diameter: 100 ⁇ m, made of diamond) and a smooth indenter at 25 ° C., a compression speed of 0.3 mN / sec, and a maximum test load of 20 mN.
  • the load value (N) and compression displacement (mm) at this time are measured. From the measured value obtained, the compression elastic modulus can be obtained by the following formula.
  • the micro compression tester for example, “Fischer Scope H-100” manufactured by Fischer is used.
  • the ratio of the (111) plane in the X-ray diffraction of the protrusion is preferably 50% or more.
  • FIG. 1 is a cross-sectional view schematically showing metal-containing particles according to the first embodiment of the present invention.
  • the metal-containing particle 1 includes a base particle 2 and a metal part 3.
  • the metal part 3 is disposed on the surface of the base particle 2.
  • the metal-containing particle 1 is a coated particle in which the surface of the base particle 2 is coated with the metal part 3.
  • the metal part 3 is a continuous film.
  • the metal-containing particle 1 has a plurality of protrusions 1 a on the outer surface of the metal part 3.
  • the metal part 3 has a plurality of protrusions 3a on the outer surface.
  • the shape of the plurality of protrusions 1a and 3a is a tapered needle shape, and is a conical shape in the present embodiment. In the present embodiment, the tips of the protrusions 1a and 3a can be melted at 400 ° C. or lower.
  • the metal part 3 has a first part and a second part that is thicker than the first part. A portion excluding the plurality of protrusions 1 a and 3 a is the first portion of the metal portion 3.
  • the plurality of protrusions 1a and 3a are the second part where the metal part 3 is thick.
  • FIG. 2 is a cross-sectional view schematically showing metal-containing particles according to the second embodiment of the present invention.
  • the metal-containing particle 1 ⁇ / b> A includes a base particle 2 and a metal part 3 ⁇ / b> A.
  • the metal part 3 ⁇ / b> A is disposed on the surface of the base particle 2.
  • the metal-containing particle 1A has a plurality of protrusions 1Aa on the outer surface of the metal portion 3A.
  • the metal portion 3A has a plurality of protrusions 3Aa on the outer surface.
  • the shape of the plurality of protrusions 1Aa and 3Aa is a tapered needle shape, and is a paraboloid in this embodiment. In the present embodiment, the tips of the protrusions 1Aa and 3Aa can be melted at 400 ° C. or lower.
  • the shape of the plurality of protrusions in the metal part is preferably a tapered needle shape, may be a conical shape, or may be a paraboloidal shape. Good.
  • FIG. 3 is a cross-sectional view schematically showing metal-containing particles according to the third embodiment of the present invention.
  • the metal-containing particle 1B includes a base particle 2 and a metal part 3B.
  • the metal part 3B is disposed on the surface of the base particle 2.
  • the metal-containing particle 1B has a plurality of protrusions 1Ba on the outer surface of the metal portion 3B.
  • the metal part 3B has a plurality of protrusions 3Ba on the outer surface.
  • the shape of the plurality of protrusions 1Ba and 3Ba is a partial shape of a sphere.
  • the metal part 3B has metal particles 3BX embedded so as to be partially exposed on the outer surface.
  • the exposed portions of the metal particles 3BX constitute the protrusions 1Ba and 3Ba.
  • the tips of the protrusions 1Ba and 3Ba can be melted at 400 ° C. or lower.
  • the shape of the protrusion may not be a tapered needle shape, and may be, for example, a shape of a part of a sphere.
  • FIG. 4 is a cross-sectional view schematically showing metal-containing particles according to the fourth embodiment of the present invention.
  • the metal-containing particle 1 ⁇ / b> C includes a base particle 2 and a metal part 3 ⁇ / b> C.
  • the metal-containing particle 1 and the metal-containing particle 1C are different only in the metal part. That is, in the metal-containing particle 1, the metal part 3 having a single layer structure is formed, whereas in the metal-containing particle 1C, the metal part 3C having a two-layer structure is formed.
  • the metal part 3C has a first metal part 3CA and a second metal part 3CB.
  • the first and second metal parts 3CA and 3CB are arranged on the surface of the base particle 2. 1st metal part 3CA is arrange
  • the outer shape of the first metal part 3CA is spherical.
  • the metal-containing particle 1C has a plurality of protrusions 1Ca on the outer surface of the metal portion 3C.
  • the metal portion 3C has a plurality of protrusions 3Ca on the outer surface.
  • Second metal portion 3CB has a plurality of protrusions on the outer surface.
  • the shape of the plurality of protrusions 1Ca and 3Ca is a tapered needle shape, and is a conical shape in the present embodiment. In the present embodiment, the tips of the protrusions 1Ca and 3Ca can be melted at 400 ° C. or lower.
  • the inner first metal part may have a plurality of protrusions on the outer surface.
  • FIG. 5 is a cross-sectional view schematically showing metal-containing particles according to the fifth embodiment of the present invention.
  • the metal-containing particle 1D includes a base particle 2 and a metal part 3D.
  • the metal part 3D is disposed on the surface of the base particle 2.
  • the metal-containing particle 1D has a plurality of protrusions 1Da on the outer surface of the metal portion 3D.
  • the metal-containing particle 1D has a plurality of convex portions (first protrusions) 3Da on the outer surface of the metal portion 3D.
  • the metal portion 3D has a plurality of convex portions (first protrusions) 3Da on the outer surface.
  • the metal part 3D has a protrusion 3Db (second protrusion) smaller than the protrusion (first protrusion) 3Da on the outer surface of the protrusion (first protrusion) 3Da.
  • the protrusion (first protrusion) 3Da and the protrusion 3Db (second protrusion) are integrated and connected.
  • the tip diameter of the protrusion 3Db (second protrusion) is small, and the tip of the protrusion 3Db (second protrusion) can be melted at 400 ° C. or lower.
  • FIG. 6 is a cross-sectional view schematically showing metal-containing particles according to the sixth embodiment of the present invention.
  • the metal-containing particle 1E includes a base particle 2, a metal part 3E, and a core substance 4E.
  • the metal part 3E is disposed on the surface of the base particle 2.
  • the metal-containing particle 1E has a plurality of protrusions 1Ea on the outer surface of the metal portion 3E.
  • the metal-containing particle 1E has a plurality of convex portions (first protrusions) 3Ea on the outer surface of the metal portion 3E.
  • the metal portion 3E has a plurality of convex portions (first protrusions) 3Ea on the outer surface.
  • the metal part 3E has a protrusion 3Eb (second protrusion) smaller than the protrusion (first protrusion) 3Ea on the outer surface of the protrusion (first protrusion) 3Ea.
  • the protrusion (first protrusion) 3Ea and the protrusion 3Eb (second protrusion) are integrated and connected.
  • the tip diameter of the protrusion 3Eb (second protrusion) is small, and the tip of the protrusion 3Eb (second protrusion) can be melted at 400 ° C. or less.
  • a plurality of core substances 4E are arranged on the outer surface of the base particle 2. Several core substance 4E is arrange
  • the metal-containing particle may include a plurality of core substances that protrude the outer surface of the metal part.
  • FIG. 7 is a cross-sectional view schematically showing metal-containing particles according to the seventh embodiment of the present invention.
  • the metal-containing particle 1 ⁇ / b> F includes a base particle 2 and a metal part 3 ⁇ / b> F.
  • the metal part 3F is disposed on the surface of the base particle 2.
  • the metal-containing particle 1F has a plurality of protrusions 1Fa on the outer surface of the metal portion 3F.
  • the metal part 3F has a protrusion 3Fb (second protrusion) smaller than the protrusion (first protrusion) 3Fa on the outer surface of the protrusion (first protrusion) 3Fa.
  • the protrusion (first protrusion) 3Fa and the protrusion 3Fb (second protrusion) are not integrated.
  • the tip diameter of the protrusion 3Fb (second protrusion) is small, and the tip of the protrusion 3Fb (second protrusion) can be melted at 400 ° C. or lower.
  • FIG. 8 is a cross-sectional view schematically showing metal-containing particles according to the eighth embodiment of the present invention.
  • the metal-containing particle 1G includes a base particle 2 and a metal portion 3G.
  • the metal part 3G has a first metal part 3GA and a second metal part 3GB.
  • the first and second metal parts 3GA and 3GB are arranged on the surface of the base particle 2.
  • a first metal part 3GA is arranged between the base particle 2 and the second metal part 3GB. Accordingly, the first metal part 3GA is arranged on the surface of the base particle 2, and the second metal part 3GB is arranged on the outer surface of the first metal part 3GA.
  • the metal part 3G is disposed on the surface of the base particle 2.
  • the metal-containing particle 1G has a plurality of protrusions 1Ga on the outer surface of the metal portion 3G.
  • the metal-containing particle 1G has a plurality of convex portions (first protrusions) 3Ga on the outer surface of the metal portion 3G.
  • the metal part 3G has a protrusion 3Gb (second protrusion) smaller than the protrusion (first protrusion) 3Ga on the outer surface of the protrusion (first protrusion) 3Ga.
  • An interface exists between the protrusion (first protrusion) 3Ga and the protrusion 3Gb (second protrusion).
  • the tip diameter of the protrusion 3Gb (second protrusion) is small, and the tip of the protrusion 3Gb (second protrusion) can be melted at 400 ° C. or lower.
  • FIGS. 11 to 14 show images of actually produced metal-containing particles.
  • the metal-containing particles shown in FIGS. 11 to 14 have a plurality of protrusions on the outer surface of the metal portion, and the tips of the plurality of protrusions can be melted at 400 ° C. or less.
  • the metal part has a plurality of protrusions on the outer surface, and has protrusions smaller than the protrusions on the outer surface of the protrusions.
  • FIG. 18 is a particle solidified after melting the tip of the protrusion of the metal part of the metal-containing particle shown in FIG.
  • (meth) acryl means one or both of “acryl” and “methacryl”
  • (meth) acrylate means one or both of “acrylate” and “methacrylate”. means.
  • the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles.
  • the base particle may have a core and a shell disposed on the surface of the core, or may be a core-shell particle.
  • the substrate particles are preferably substrate particles excluding metal particles, and more preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles.
  • the base material particles are more preferably resin particles or organic-inorganic hybrid particles, and may be resin particles or organic-inorganic hybrid particles. By using these preferable base particles, metal-containing particles suitable for the connection application of two connection target members can be obtained.
  • the substrate particles are resin particles or organic / inorganic hybrid particles
  • the metal-containing particles are easily deformed, and the flexibility of the metal-containing particles is increased. For this reason, shock absorption becomes high after the connection.
  • the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Alkylene terephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene Oxide, polyacetal, polyimide, polyamideimide, polyether ether Tons, polyethersulfone, and polymers such as obtained by a variety of polymerizable monomer having an ethylene
  • the resin particles having the physical properties at the time of compression suitable for the connection application of the two connection target members can be designed and synthesized, and the hardness of the base particles can be easily controlled within a suitable range
  • the resin particles The resin for forming is preferably a polymer obtained by polymerizing one or more polymerizable monomers having a plurality of ethylenically unsaturated groups.
  • the resin particles are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group, as the polymerizable monomer having an ethylenically unsaturated group, a non-crosslinkable monomer and And a crosslinkable monomer.
  • non-crosslinkable monomer examples include styrene monomers such as styrene and ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylate compounds such as meth) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, etc.
  • Oxygen atom-containing (meth) acrylate compounds Nitrile-containing monomers such as (meth) acrylonitrile; Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate Vinyl ester compounds; unsaturated hydrocarbons such as ethylene, propylene, isoprene, and butadiene; halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene Etc.
  • Nitrile-containing monomers such as (meth) acrylonitrile
  • Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether
  • Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stea
  • crosslinkable monomer examples include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylate compounds such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) sia Silane-
  • the resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
  • the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal particles
  • examples of the inorganic material for forming the substrate particles include silica, alumina, barium titanate, zirconia, and carbon black.
  • the inorganic substance is preferably not a metal.
  • the particles formed by the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle
  • examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell disposed on the surface of the core.
  • the core is preferably an organic core.
  • the shell is preferably an inorganic shell.
  • the substrate particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core.
  • Examples of the material for forming the inorganic shell include inorganic substances for forming the above-described base material particles.
  • the material for forming the inorganic shell is preferably silica.
  • the inorganic shell is preferably formed on the surface of the core by forming a metal alkoxide into a shell-like material by a sol-gel method and then firing the shell-like material.
  • the metal alkoxide is preferably a silane alkoxide.
  • the inorganic shell is preferably formed of a silane alkoxide.
  • the particle size of the core is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, particularly preferably 20 ⁇ m or less, and most preferably 10 ⁇ m or less. It is.
  • the particle diameter of the core is not less than the above lower limit and not more than the above upper limit, it can be suitably used for the connection application of two connection target members.
  • the particle diameter of the core is not less than the lower limit and not more than the upper limit, when two connection target members are connected using the metal-containing particles, the contact area between the metal-containing particles and the connection target member is sufficient. And the agglomerated metal-containing particles are hardly formed when the metal part is formed.
  • the interval between the two connection target members connected via the metal-containing particles does not become too large, and the metal portion is difficult to peel off from the surface of the substrate particles.
  • the particle diameter of the core means a diameter when the core is a true sphere, and means a maximum diameter when the core is a shape other than a true sphere.
  • the particle size of a core means the average particle size which measured the core with the arbitrary particle size measuring apparatus.
  • a particle size distribution measuring machine using principles such as laser light scattering, electrical resistance value change, and image analysis after imaging can be used.
  • the thickness of the shell is preferably 100 nm or more, more preferably 200 nm or more, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
  • the shell can be suitably used for connecting two connection target members.
  • the thickness of the shell is an average thickness per base particle.
  • the thickness of the shell can be controlled by controlling the sol-gel method.
  • the substrate particles are metal particles
  • examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium.
  • the substrate particles are preferably not metal particles.
  • the particle diameter of the substrate particles is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, still more preferably 1 ⁇ m or more, still more preferably 1.5 ⁇ m or more, particularly preferably 2 ⁇ m or more, preferably 1000 ⁇ m. Below, more preferably 500 ⁇ m or less, still more preferably 400 ⁇ m or less, still more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, still more preferably 30 ⁇ m or less, particularly preferably 5 ⁇ m or less, and most preferably 3 ⁇ m or less. When the particle diameter of the substrate particles is not less than the above lower limit, the connection reliability is further enhanced.
  • the metal-containing particles are easily compressed, and the connection reliability is further enhanced.
  • the particle diameter of the substrate particles indicates a diameter when the substrate particles are spherical, and indicates a maximum diameter when the substrate particles are not spherical.
  • the substrate particles are particles containing silicone resin (silicone Particles).
  • the material of the substrate particles preferably contains a silicone resin.
  • the material of the silicone particles is preferably a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms, or having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms. It is preferably a silane compound having a radical polymerizable group or a silane compound having both radically polymerizable groups. When these materials are reacted, a siloxane bond is formed. In the resulting silicone particles, radically polymerizable groups and hydrophobic groups having 5 or more carbon atoms generally remain.
  • silicone particles having a primary particle size of 0.1 ⁇ m or more and 500 ⁇ m or less can be easily obtained, and the chemical resistance of the silicone particles is increased and the moisture permeability is decreased. be able to.
  • the radical polymerizable group is preferably directly bonded to a silicon atom.
  • the silane compound which has the said radical polymerizable group only 1 type may be used and 2 or more types may be used together.
  • the silane compound having a radical polymerizable group is preferably an alkoxysilane compound.
  • examples of the silane compound having a radical polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, divinylmethoxyvinylsilane, divinylethoxyvinylsilane, divinyldimethoxysilane, divinyldiethoxysilane, and 1 , 3-divinyltetramethyldisiloxane and the like.
  • the hydrophobic group having 5 or more carbon atoms is preferably directly bonded to a silicon atom. Only 1 type may be used for the said silane compound which has a C5 or more hydrophobic group, and 2 or more types may be used together.
  • the silane compound having a hydrophobic group having 5 or more carbon atoms is preferably an alkoxysilane compound.
  • Examples of the silane compound having a hydrophobic group having 5 or more carbon atoms include phenyltrimethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, dimethylmethoxyphenylsilane, dimethylethoxyphenylsilane, hexaphenyldisiloxane, 1,3, 3,5-tetramethyl-1,1,5,5-tetraphenyltrisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, hexaphenylcyclotrisiloxane, phenyl Examples include tris (trimethylsiloxy) silane and octaphenylcyclotetrasiloxane.
  • the radical polymerizable group is preferably directly bonded to a silicon atom, and the hydrophobic group having 5 or more carbon atoms is bonded to a silicon atom. Direct bonding is preferred.
  • the silane compound having a radical polymerizable group and having a hydrophobic group having 5 or more carbon atoms only one kind may be used, or two or more kinds may be used in combination.
  • silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms examples include phenylvinyldimethoxysilane, phenylvinyldiethoxysilane, phenylmethylvinylmethoxysilane, phenylmethylvinylethoxysilane, and diphenylvinylmethoxysilane. , Diphenylvinylethoxysilane, phenyldivinylmethoxysilane, phenyldivinylethoxysilane, 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane, and the like.
  • the silane compound having the radical polymerizable group and the silane compound having a hydrophobic group having 5 or more carbon atoms are preferably used in a weight ratio of 1: 1 to 1:20, more preferably 1: 5 to 1:15.
  • the number of radical polymerizable groups and the number of hydrophobic groups having 5 or more carbon atoms are preferably 1: 0.5 to 1:20, and 1: 1 to More preferably, it is 1:15.
  • the silicone particles have two methyl groups bonded to one silicon atom.
  • the material of the silicone particle contains a silane compound in which two methyl groups are bonded to one silicon atom.
  • the silicone particles described above can be obtained by using a radical polymerization initiator. It is preferable to react to form a siloxane bond. In general, it is difficult to obtain silicone particles having a primary particle size of 0.1 ⁇ m or more and 500 ⁇ m or less using a radical polymerization initiator, and it is particularly preferable to obtain silicone particles having a primary particle size of 100 ⁇ m or less. Have difficulty. In contrast, even when a radical polymerization initiator is used, silicone particles having a primary particle diameter of 0.1 ⁇ m or more and 500 ⁇ m or less can be obtained by using the silane compound, and primary particles of 100 ⁇ m or less. Silicone particles having a diameter can also be obtained.
  • the silane compound can be polymerized using a radical polymerization initiator without using a metal catalyst.
  • the metal particles can be prevented from being contained in the silicone particles, the content of the metal catalyst in the silicone particles can be reduced, the chemical resistance is effectively increased, and the moisture permeability is effectively increased.
  • the 10% K value can be controlled within a suitable range.
  • the method for producing the silicone particles include a method of producing a silicone particle by performing a polymerization reaction of a silane compound by a suspension polymerization method, a dispersion polymerization method, a miniemulsion polymerization method, an emulsion polymerization method, or the like. After the polymerization of the silane compound proceeds to obtain an oligomer, a polymerization reaction of the silane compound that is a polymer (such as an oligomer) is performed by a suspension polymerization method, a dispersion polymerization method, a miniemulsion polymerization method, or an emulsion polymerization method, Silicone particles may be produced.
  • a silane compound having a vinyl group bonded to a silicon atom at the terminal may be obtained by polymerizing a silane compound having a vinyl group.
  • a silane compound having a phenyl group may be polymerized to obtain a silane compound having a phenyl group bonded to a silicon atom in the side chain as a polymer (such as an oligomer).
  • a silane compound having a vinyl group and a silane compound having a phenyl group are polymerized to form a polymer (such as an oligomer) having a vinyl group bonded to a silicon atom at a terminal and a phenyl group bonded to a silicon atom in a side chain You may obtain the silane compound which has this.
  • the silicone particles may have a plurality of particles on the outer surface.
  • the silicone particle may include a silicone particle main body and a plurality of particles arranged on the surface of the silicone particle main body.
  • the plurality of particles include silicone particles and spherical silica. The presence of the plurality of particles can suppress aggregation of the silicone particles.
  • the tip of the protrusion of the metal part can be melted at 400 ° C. or lower. From the viewpoint of suppressing the energy consumption during heating by lowering the melting temperature and further suppressing the thermal deterioration of the connection target member, the tip of the protrusion of the metal part can be melted at 350 ° C. or lower. It is more preferable that it can be melted at 300 ° C. or less, it is more preferable that it can be melted at 250 ° C. or less, and it is particularly preferable that it can be melted at 200 ° C. or less.
  • the melting temperature at the tip of the protrusion can be controlled by the type of metal at the tip of the protrusion and the shape of the tip of the protrusion.
  • the melting point of the base of the convex part, the center position of the height of the protrusion, the base part of the protrusion, and the center position of the height of the protrusion may exceed 200 ° C or exceed 250 ° C. Or may exceed 300 ° C, may exceed 350 ° C, or may exceed 400 ° C.
  • the metal part, the convex part, and the protrusion may have a part exceeding 200 ° C., may have a part exceeding 250 ° C., and may have a part exceeding 300 ° C. , May have a portion exceeding 350 ° C., or may have a portion exceeding 400 ° C.
  • the material for the metal part is not particularly limited.
  • the material of the metal part preferably contains a metal.
  • the metal include gold, silver, palladium, rhodium, iridium, lithium, copper, platinum, zinc, iron, tin, lead, ruthenium, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, and thallium. , Germanium, cadmium, silicon, and alloys thereof.
  • the metal include tin-doped indium oxide (ITO).
  • the material of the metal part is selected so that the tip of the protrusion of the metal part can be melted at 400 ° C. or less.
  • the material of the protrusion preferably contains silver, copper, gold, palladium, tin, indium or zinc.
  • the material of the protrusion may not contain tin.
  • the material of the metal part is not solder. It can suppress that the whole metal part melt
  • the material of the metal part may not contain tin.
  • the material of the metal part is silver, copper, gold, palladium, tin, indium, zinc, nickel, cobalt, iron, tungsten, molybdenum, ruthenium, platinum, rhodium, iridium , Phosphorus or boron is preferable, silver, copper, gold, palladium, tin, indium or zinc is more preferable, and silver is further preferable.
  • these preferable materials only 1 type may be used and 2 or more types may be used together.
  • the silver may be contained as a single silver or silver oxide. Examples of silver oxide include Ag 2 O and AgO.
  • the content of silver is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 100% by weight or less, more preferably 90% by weight or less, % By weight or less, 60% by weight or less, 40% by weight or less, 20% by weight or less, or 10% by weight or less may be used.
  • the silver content is not less than the above lower limit and not more than the above upper limit, the bonding strength is increased and the connection reliability is further enhanced.
  • the copper may be contained as a simple copper or copper oxide.
  • the content of copper is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 100% by weight or less, more preferably 90% by weight or less, % By weight or less, 60% by weight or less, 40% by weight or less, 20% by weight or less, or 10% by weight or less may be used.
  • the copper content is not less than the above lower limit and not more than the above upper limit, the bonding strength is increased and the connection reliability is further enhanced.
  • the metal part may be formed of one layer.
  • the metal part may be formed of a plurality of layers.
  • the outer surface of the metal part may be rust-proofed.
  • the metal-containing particles may have a rust preventive film on the outer surface of the metal part.
  • Examples of the rust prevention treatment include a method of arranging a rust inhibitor on the outer surface of the metal part, a method of alloying the outer surface of the metal part to improve corrosion resistance, a method of coating a high corrosion resistant metal film on the outer surface of the metal part, etc. Can be mentioned.
  • the rust preventive include nitrogen-containing heterocyclic compounds such as benzotriazole compounds and imidazole compounds; sulfur-containing compounds such as mercaptan compounds, thiazole compounds and organic disulfide compounds; and phosphorus-containing compounds such as organic phosphate compounds.
  • sulfur-resistant agents, rust inhibitors and discoloration inhibitors include nitrogen-containing heterocyclic compounds such as benzotriazole compounds and imidazole compounds; sulfur-containing compounds such as mercaptan compounds, thiazole compounds and organic disulfide compounds; and organic phosphate compounds. Examples thereof include phosphorus-containing compounds.
  • the outer surface of the metal part is preferably rust-proofed with a compound having an alkyl group having 6 to 22 carbon atoms.
  • the surface of the metal part may be rust-proofed with a compound not containing phosphorus, or may be rust-proofed with a compound having an alkyl group having 6 to 22 carbon atoms and not containing phosphorus.
  • the outer surface of the metal part is preferably rust-proofed with an alkyl phosphate compound or an alkyl thiol.
  • the rust preventive film is preferably formed of a compound having an alkyl group having 6 to 22 carbon atoms (hereinafter also referred to as compound A).
  • the outer surface of the metal part is preferably surface-treated with the compound A.
  • the carbon number of the alkyl group is 6 or more, rust is more unlikely to occur in the entire metal part.
  • the carbon number of the alkyl group is 22 or less, the conductivity of the metal-containing particles is increased.
  • the alkyl group in the compound A preferably has 16 or less carbon atoms.
  • the alkyl group may have a linear structure or a branched structure.
  • the alkyl group preferably has a linear structure.
  • the compound A is not particularly limited as long as it has an alkyl group having 6 to 22 carbon atoms.
  • the compound A has a phosphate ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof, a phosphite ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof, and an alkyl group having 6 to 22 carbon atoms.
  • An alkoxysilane, an alkylthiol having an alkyl group having 6 to 22 carbon atoms, or a dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms is preferable.
  • the compound A having an alkyl group having 6 to 22 carbon atoms is preferably a phosphate ester or a salt thereof, a phosphite ester or a salt thereof, an alkoxysilane, an alkylthiol, or a dialkyl disulfide.
  • the compound A is preferably the phosphate ester or salt thereof, phosphite ester or salt thereof, or alkylthiol, and the phosphate ester or salt thereof, Or it is more preferable that it is a phosphite or its salt.
  • the said compound A only 1 type may be used and 2 or more types may be used together.
  • the compound A preferably has a reactive functional group capable of reacting with the outer surface of the metal part.
  • the metal-containing particles include an insulating substance disposed on the outer surface of the metal part
  • the compound A preferably has a reactive functional group capable of reacting with the insulating substance.
  • the rust preventive film is preferably chemically bonded to the metal part.
  • the rust preventive film is preferably chemically bonded to the insulating material. More preferably, the rust preventive film is chemically bonded to both the metal part and the insulating material. Due to the presence of the reactive functional group and due to the chemical bond, the rust preventive film is less likely to be peeled off. As a result, the rust is less likely to be generated in the metal part, and the insulating material is exposed from the surface of the metal-containing particles. However, it becomes more difficult to detach unintentionally.
  • Examples of the phosphate ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof include, for example, hexyl phosphate, heptyl phosphate, monooctyl phosphate, monononyl phosphate, monodecyl phosphate, Monoundecyl phosphate, monododecyl phosphate, monotridecyl phosphate, monotetradecyl phosphate, monopentadecyl phosphate, monohexyl phosphate monosodium salt, monoheptyl phosphate monosodium Salt, monooctyl phosphate monosodium salt, monononyl phosphate monosodium salt, monodecyl phosphate monosodium salt, monoundecyl phosphate monosodium salt, monododecyl phosphate monosodium salt Phosphoric acid mono-tridecyl ester monosodium salt,
  • Examples of the phosphite having a C 6-22 alkyl group or a salt thereof include, for example, hexyl phosphite, heptyl phosphite, monooctyl phosphite, monononyl phosphite, phosphite Phosphoric acid monodecyl ester, phosphorous acid monoundecyl ester, phosphorous acid monododecyl ester, phosphorous acid monotridecyl ester, phosphorous acid monotetradecyl ester, phosphorous acid monopentadecyl ester, phosphorous acid monohexyl Ester monosodium salt, phosphorous acid monoheptyl ester monosodium salt, phosphorous acid monooctyl ester monosodium salt, phosphorous acid monononyl ester monosodium salt, phosphorous acid monodecyl ester monosodium salt, phospho
  • alkoxysilane having an alkyl group having 6 to 22 carbon atoms examples include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltri Methoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxy Examples include silane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane
  • alkyl thiol having an alkyl group having 6 to 22 carbon atoms examples include hexyl thiol, heptyl thiol, octyl thiol, nonyl thiol, decyl thiol, undecyl thiol, dodecyl thiol, tridecyl thiol, tetradecyl thiol, pentadecyl. Examples include thiol and hexadecyl thiol.
  • the alkyl thiol preferably has a thiol group at the end of the alkyl chain.
  • dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms examples include dihexyl disulfide, diheptyl disulfide, dioctyl disulfide, dinonyl disulfide, didecyl disulfide, diundecyl disulfide, didodecyl disulfide, ditridecyl disulfide, ditetradecyl disulfide. Examples include decyl disulfide, dipentadecyl disulfide, and dihexadecyl disulfide.
  • the outer surface of the metal part is made of any layer of a sulfur-containing compound, a benzotriazole compound, or a polyoxyethylene ether surfactant mainly composed of a sulfide compound or a thiol compound. It is preferable that the sulfidation treatment is performed. A rust preventive film can be formed on the outer surface of the metal part by the anti-sulfurization treatment.
  • Examples of the sulfide compound include about 6 to 40 carbon atoms (preferably carbon number) such as dihexyl sulfide, diheptyl sulfide, dioctyl sulfide, didecyl sulfide, didodecyl sulfide, ditetradecyl sulfide, dihexadecyl sulfide, and dioctadecyl sulfide.
  • dialkyl sulfide alkyl sulfide
  • aromatic having about 12 to 30 carbon atoms such as diphenyl sulfide, phenyl-p-tolyl sulfide, 4,4-thiobisbenzenethiol, etc.
  • Sulfides; thiodicarboxylic acids such as 3,3′-thiodipropionic acid and 4,4′-thiodibutanoic acid.
  • the sulfide compound is particularly preferably a dialkyl sulfide.
  • thiol compound examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-methyl-2-propanethiol, octadecylthiol, and the like, and about 4 to 40 carbon atoms (more preferably 6 to 20). Degree) linear or branched alkylthiol and the like. Moreover, the compound etc. with which the hydrogen atom couple
  • benzotriazole compounds include benzotriazole, benzotriazole salts, methylbenzotriazole, carboxybenzotriazole, and benzotriazole derivatives.
  • anti-discoloring agent examples include trade names “AC-20”, “AC-70” and “AC-80” manufactured by Kitaike Sangyo Co., Ltd., trade names “ENTEC CU-56” manufactured by Meltex, and Daiwa Kasei.
  • the method for forming the metal part on the surface of the substrate particle is not particularly limited.
  • a method for forming a metal part for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating the surface of base particles with metal powder or a paste containing metal powder and a binder Etc. Since formation of a metal part is simple, the method by electroless plating is preferable.
  • Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
  • a method by electroless high-purity nickel plating using hydrazine as a reducing agent, a method by electroless palladium-nickel alloy using hydrazine as a reducing agent, an electroless CoNiP alloy plating method using a hypophosphite compound as a reducing agent examples thereof include a method by electroless silver plating using hydrazine as a reducing agent, and a method by electroless copper-nickel-phosphorus alloy plating using a hypophosphite compound as a reducing agent.
  • a catalytic step and an electroless plating step are performed.
  • an example of a method of forming an alloy plating layer containing copper and nickel and a needle-like protrusion tapered on the outer surface of the metal part on the surface of the resin particle by electroless plating will be described.
  • a catalyst serving as a starting point for forming a plating layer by electroless plating is formed on the surface of the resin particles.
  • the surface of the resin particles is activated with an acid solution or an alkali solution
  • a phosphorus-containing reducing agent is used as the reducing agent.
  • the metal part containing phosphorus can be formed by using a phosphorus containing reducing agent as said reducing agent.
  • a hypophosphite compound is included as a reducing agent. It is preferable to use a copper-nickel-phosphorus alloy plating solution containing a nickel-containing compound as a reaction initiation metal catalyst and containing a nonionic surfactant.
  • a copper-nickel-phosphorus alloy By immersing resin particles in a copper-nickel-phosphorus alloy plating bath, a copper-nickel-phosphorus alloy can be deposited on the surface of the resin particles on which the catalyst is formed. A metal part can be formed.
  • Examples of the copper-containing compound include copper sulfate, cupric chloride, and copper nitrate.
  • the copper-containing compound is preferably copper sulfate.
  • nickel-containing compound examples include nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate, and nickel nitrate.
  • the nickel-containing compound is preferably nickel sulfate.
  • Examples of the phosphorus-containing reducing agent include hypophosphorous acid and sodium hypophosphite.
  • a boron-containing reducing agent may be used.
  • Examples of the boron-containing reducing agent include dimethylamine borane, sodium borohydride, and potassium borohydride.
  • the complexing agents include monocarboxylic acid complexing agents such as sodium acetate and sodium propionate, dicarboxylic acid complexing agents such as disodium malonate, tricarboxylic acid complexing agents such as disodium succinate, lactic acid, DL-apple Hydroxy acid complexing agents such as acid, Rochelle salt, sodium citrate and sodium gluconate, amino acid complexing agents such as glycine and EDTA, amine complexing agents such as ethylenediamine, organic acid complexing agents such as maleic acid, or These salts are preferred. Only 1 type may be used for these preferable complexing agents, and 2 or more types may be used together.
  • the surfactant examples include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant, and a nonionic surfactant is particularly preferable.
  • Preferred nonionic surfactants are polyethers containing ether oxygen atoms.
  • Preferred nonionic surfactants include polyoxyethylene lauryl ether, polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene nonylphenyl ether, polyoxyethylene polyoxypropylene alkylamine, And polyoxyalkylene adducts of ethylenediamine and the like.
  • polyoxyethylene monoalkyl ethers such as polyoxyethylene monobutyl ether, polyoxypropylene monobutyl ether, polyoxyethylene polyoxypropylene glycol monobutyl ether, polyethylene glycol or phenol ethoxylate.
  • the said surfactant only 1 type may be used and 2 or more types may be used together.
  • Polyethylene glycol having a molecular weight of about 1000 (for example, 500 or more and 2000 or less) is particularly preferable.
  • the amount of the copper compound used is preferably 2 to 100 times in molar ratio to the nickel compound.
  • a protrusion having a needle shape can be obtained without using the above-described nonionic surfactant or the like.
  • a nonionic surfactant it is preferable to use a nonionic surfactant, and it is particularly preferable to use polyethylene glycol having a molecular weight of about 1000 (for example, 500 or more and 2000 or less). preferable.
  • the ratio of the average height (b) of the plurality of protrusions to the average diameter (c) of the base portions of the plurality of protrusions depends on the thickness of the metal part, It can be controlled by the immersion time in the plating bath.
  • the plating temperature is preferably 30 ° C. or higher, preferably 100 ° C. or lower, and the immersion time in the plating bath is preferably 5 minutes or longer.
  • a catalyst serving as a starting point for forming a plating layer by electroless plating is formed on the surface of the resin particles.
  • the surface of the resin particles is activated with an acid solution or an alkali solution
  • a phosphorus-containing reducing agent is used as the reducing agent.
  • the metal part containing phosphorus can be formed by using a phosphorus containing reducing agent as said reducing agent.
  • a silver plating solution containing hydrazine, a nonionic surfactant and a sulfur-containing organic compound as a reducing agent Is preferably used.
  • silver By immersing the resin particles in the silver plating bath, silver can be deposited on the surface of the resin particles on which the catalyst is formed, and a metal part containing silver can be formed.
  • silver-containing compound potassium silver cyanide, silver nitrate, silver thiosulfate sodium, silver gluconate, silver-cysteine complex, and silver methanesulfonate are preferable.
  • reducing agent examples include hydrazine, sodium hypophosphite, dimethylamine borane, sodium borohydride and potassium borohydride, formalin, glucose and the like.
  • reducing agent for forming the protrusion having a needle shape hydrazine monohydrate, hydrazine hydrochloride, and hydrazine sulfate are preferable.
  • the complexing agent is a monocarboxylic acid complexing agent such as sodium acetate or sodium propionate, a dicarboxylic acid complexing agent such as disodium malonate, a tricarboxylic acid complexing agent such as disodium succinate, lactic acid, DL-malic acid, Rochelle salt, hydroxy acid complexing agents such as sodium citrate and sodium gluconate, amino acid complexing agents such as glycine and EDTA, amine complexing agents such as ethylenediamine, and organic acids such as maleic acid
  • a complexing agent or a salt thereof is preferable. Only 1 type may be used for these preferable complexing agents, and 2 or more types may be used together.
  • the surfactant examples include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant, and a nonionic surfactant is particularly preferable.
  • Preferred nonionic surfactants are polyethers containing ether oxygen atoms.
  • Preferred nonionic surfactants include polyoxyethylene lauryl ether, polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene nonylphenyl ether, polyoxyethylene polyoxypropylene alkylamine, And polyoxyalkylene adducts of ethylenediamine and the like.
  • polyoxyethylene monoalkyl ethers such as polyoxyethylene monobutyl ether, polyoxypropylene monobutyl ether, polyoxyethylene polyoxypropylene glycol monobutyl ether, polyethylene glycol or phenol ethoxylate.
  • the said surfactant only 1 type may be used and 2 or more types may be used together.
  • Polyethylene glycol having a molecular weight of about 1000 (for example, 500 or more and 2000 or less) is particularly preferable.
  • a protrusion having a needle shape can be obtained without using the above-described nonionic surfactant or the like.
  • a nonionic surfactant it is preferable to use a nonionic surfactant, and it is particularly preferable to use polyethylene glycol having a molecular weight of about 1000 (for example, 500 or more and 2000 or less). preferable.
  • Examples of the sulfur-containing organic compound include organic compounds having a sulfide or sulfonic acid group, thiourea compounds, and benzothiazole compounds.
  • Examples of the organic compound having a sulfide or sulfonic acid group include N, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester, 3-mercapto-propylsulfonic acid- (3-sulfopropyl) ester, 3-mercapto- Propylsulfonic acid sodium salt, 3-mercapto-1-propanesulfonic acid potassium salt, carbonic acid-dithio-o-ethyl ester, bissulfopropyl disulfide, bis- (3-sulfopropyl) -disulfide disodium salt, 3- ( Benzothiazolyl-s-thio) propylsulfonic acid sodium salt, pyridiniumpropylsulfobetaine, 1-s
  • a protrusion having a needle shape can be obtained without using the above-described sulfur-containing organic compound.
  • a sulfur-containing organic compound is preferably used, and thiourea is particularly preferably used.
  • the ratio of the average height (b) of the plurality of protrusions to the average diameter (c) of the base portions of the plurality of protrusions depends on the thickness of the metal part, It can be controlled by the immersion time in the plating bath.
  • the plating temperature is preferably 30 ° C. or higher, preferably 100 ° C. or lower, and the immersion time in the plating bath is preferably 5 minutes or longer.
  • a catalyst serving as a starting point for forming a plating layer by electroless plating is formed on the surface of the resin particles.
  • the surface of the resin particles is activated with an acid solution or an alkali solution
  • a phosphorus-containing reducing agent is used as the reducing agent.
  • the metal part containing phosphorus can be formed by using a phosphorus containing reducing agent as said reducing agent.
  • a high purity nickel plating solution containing hydrazine as a reducing agent is suitably used in an electroless high purity nickel plating method using a plating solution containing a nickel-containing compound, a complexing agent and a reducing agent.
  • high-purity nickel plating By immersing resin particles in a high-purity nickel plating bath, high-purity nickel plating can be deposited on the surface of the resin particles on which the catalyst is formed, and a metal portion of high-purity nickel can be formed.
  • nickel-containing compound examples include nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate, and nickel nitrate.
  • the nickel-containing compound is preferably nickel chloride.
  • reducing agent examples include hydrazine monohydrate, hydrazine hydrochloride, and hydrazine sulfate.
  • the reducing agent is preferably hydrazine monohydrate.
  • the complexing agent examples include monocarboxylic acid complexing agents such as sodium acetate and sodium propionate, dicarboxylic acid complexing agents such as disodium malonate, tricarboxylic acid complexing agents such as disodium succinate, and lactic acid.
  • monocarboxylic acid complexing agents such as sodium acetate and sodium propionate
  • dicarboxylic acid complexing agents such as disodium malonate
  • tricarboxylic acid complexing agents such as disodium succinate
  • lactic acid DL-malic acid, Rochelle salt, hydroxy acid complexing agents such as sodium citrate and sodium gluconate, amino acid complexing agents such as glycine and EDTA, amine complexing agents such as ethylenediamine, and organic such as maleic acid
  • amino acid complexing agents such as glycine and EDTA
  • amine complexing agents such
  • the pH of the plating solution In order to form a needle-like protrusion tapering on the outer surface of the metal part, it is preferable to adjust the pH of the plating solution to 8.0 or more.
  • An electroless plating solution using hydrazine as a reducing agent is accompanied by a sharp drop in pH when nickel is reduced by an oxidation reaction of hydrazine.
  • a buffering agent such as phosphoric acid, boric acid or carbonic acid.
  • the buffering agent is preferably boric acid having a buffering effect at pH 8.0 or higher.
  • the ratio of the average height (b) of the plurality of protrusions to the average diameter (c) of the base portions of the plurality of protrusions depends on the thickness of the metal part, It can be controlled by the immersion time in the plating bath.
  • the plating temperature is preferably 30 ° C. or higher, preferably 100 ° C. or lower, and the immersion time in the plating bath is preferably 5 minutes or longer.
  • a catalyst serving as a starting point for forming a plating layer by electroless plating is formed on the surface of the resin particles.
  • the surface of the resin particles is activated with an acid solution or an alkali solution
  • a phosphorus-containing reducing agent is used as the reducing agent.
  • the metal part containing phosphorus can be formed by using a phosphorus containing reducing agent as said reducing agent.
  • a palladium-nickel alloy plating containing hydrazine as a reducing agent.
  • a liquid is preferably used.
  • palladium-nickel alloy plating By immersing resin particles in a palladium-nickel alloy plating bath, palladium-nickel alloy plating can be deposited on the surface of the resin particles on which the catalyst is formed, and a metal part of palladium-nickel can be formed. .
  • nickel-containing compound examples include nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate, and nickel nitrate.
  • the nickel-containing compound is preferably nickel sulfate.
  • the palladium-containing compound examples include dichloroethylenediamine palladium (II), palladium chloride, dichlorodiammine palladium (II), dinitrodiammine palladium (II), tetraammine palladium (II) nitrate, tetraammine palladium (II) sulfate, oxalato diammine. Palladium (II), tetraammine palladium (II) oxalate, tetraammine palladium (II) chloride, etc. are mentioned.
  • the palladium-containing compound is preferably palladium chloride.
  • the stabilizer includes a lead compound, a bismuth compound, a thallium compound, and the like. Specific examples of these compounds include sulfates, carbonates, acetates, nitrates, and hydrochlorides of metals (lead, bismuth, thallium) constituting the compounds. In consideration of the influence on the environment, a bismuth compound or a thallium compound is preferable. As for these preferable stabilizers, only 1 type may be used and 2 or more types may be used together.
  • reducing agent examples include hydrazine monohydrate, hydrazine hydrochloride, and hydrazine sulfate.
  • the reducing agent is preferably hydrazine monohydrate.
  • the complexing agent examples include monocarboxylic acid complexing agents such as sodium acetate and sodium propionate, dicarboxylic acid complexing agents such as disodium malonate, tricarboxylic acid complexing agents such as disodium succinate, and lactic acid.
  • monocarboxylic acid complexing agents such as sodium acetate and sodium propionate
  • dicarboxylic acid complexing agents such as disodium malonate
  • tricarboxylic acid complexing agents such as disodium succinate
  • lactic acid DL-malic acid, Rochelle salt, hydroxy acid complexing agents such as sodium citrate and sodium gluconate, amino acid complexing agents such as glycine and EDTA, amine complexing agents such as ethylenediamine, and organic such as maleic acid Examples include acid complexing agents.
  • the complexing agent is preferably ethylenediamine which is an amino acid complexing agent.
  • the pH of the plating solution In order to form a needle-like protrusion tapering on the outer surface of the metal part, it is preferable to adjust the pH of the plating solution from 8.0 to 10.0. When the pH is 7.5 or lower, the stability of the plating solution is lowered and bath decomposition is caused. Therefore, the pH is preferably 8.0 or higher.
  • the ratio of the average height (b) of the plurality of protrusions to the average diameter (c) of the base portions of the plurality of protrusions depends on the thickness of the metal part, It can be controlled by the immersion time in the plating bath.
  • the plating temperature is preferably 30 ° C. or higher, preferably 100 ° C. or lower, and the immersion time in the plating bath is preferably 5 minutes or longer.
  • a catalyst serving as a starting point for forming a plating layer by electroless plating is formed on the surface of the resin particles.
  • the surface of the resin particles is activated with an acid solution or an alkali solution
  • a phosphorus-containing reducing agent is used as the reducing agent.
  • the metal part containing phosphorus can be formed by using a phosphorus containing reducing agent as said reducing agent.
  • a hypophosphite compound is included as a reducing agent.
  • a cobalt-nickel-phosphorus alloy plating solution containing a cobalt-containing compound is preferably used as a reaction initiation metal catalyst for the reducing agent.
  • the cobalt-nickel-phosphorus alloy By immersing the resin particles in the cobalt-nickel-phosphorus alloy plating bath, the cobalt-nickel-phosphorus alloy can be deposited on the surface of the resin particles on which the catalyst is formed.
  • the metal part containing can be formed.
  • the cobalt-containing compound is preferably cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt acetate, or cobalt carbonate.
  • the cobalt-containing compound is more preferably cobalt sulfate.
  • nickel-containing compound examples include nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate, and nickel nitrate.
  • the nickel-containing compound is preferably nickel sulfate.
  • Examples of the phosphorus-containing reducing agent include hypophosphorous acid and sodium hypophosphite.
  • a boron-containing reducing agent may be used.
  • Examples of the boron-containing reducing agent include dimethylamine borane, sodium borohydride, and potassium borohydride.
  • the complexing agent is a monocarboxylic acid complexing agent such as sodium acetate or sodium propionate, a dicarboxylic acid complexing agent such as disodium malonate, a tricarboxylic acid complexing agent such as disodium succinate, lactic acid, DL-malic acid, Rochelle salt, hydroxy acid complexing agents such as sodium citrate and sodium gluconate, amino acid complexing agents such as glycine and EDTA, amine complexing agents such as ethylenediamine, and organic acids such as maleic acid
  • a complexing agent or a salt thereof is preferable. Only 1 type may be used for these preferable complexing agents, and 2 or more types may be used together.
  • the inorganic additive is preferably ammonium sulfate, ammonium chloride, or boric acid. As for these preferable inorganic additives, only 1 type may be used and 2 or more types may be used together. The inorganic additive is considered to act to promote precipitation of the electroless cobalt plating layer.
  • the amount of the cobalt compound used is preferably 2 to 100 times in molar ratio to the nickel compound.
  • a protrusion having a needle shape can be obtained without using the above-mentioned inorganic additive.
  • an inorganic additive it is preferable to use an inorganic additive, and it is particularly preferable to use ammonium sulfate.
  • the ratio of the average height (b) of the plurality of protrusions to the average diameter (c) of the base portions of the plurality of protrusions depends on the thickness of the metal part, It can be controlled by the immersion time in the plating bath.
  • the plating temperature is preferably 30 ° C. or higher, preferably 100 ° C. or lower, and the immersion time in the plating bath is preferably 5 minutes or longer.
  • the thickness of the entire metal part in the portion where there is no protrusion is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, particularly preferably 50 nm or more, preferably 1000 nm or less, more preferably 800 nm or less, Preferably it is 500 nm or less, Especially preferably, it is 400 nm or less.
  • the thickness of the entire metal part in the portion without the convex part is preferably 5 nm or more, more preferably 10 nm or more, further preferably 20 nm or more, particularly preferably 50 nm or more, preferably 1000 nm or less, more preferably 800 nm or less, More preferably, it is 500 nm or less, Most preferably, it is 400 nm or less.
  • the thickness of the entire metal part is equal to or more than the above lower limit, peeling of the metal part is suppressed. If the thickness of the entire metal part is less than or equal to the above upper limit, the difference in coefficient of thermal expansion between the base particle and the metal part becomes small, and the metal part becomes difficult to peel from the base particle.
  • the thickness of the metal part is the total thickness of the metal part (the total of the first and second metal parts). Thickness).
  • the thickness of the metal part in the portion of the outermost layer without the protrusion is preferably 1 nm or more, more preferably 10 nm or more, preferably 500 nm or less, more preferably 100 nm. It is as follows.
  • the thickness of the metal part in the portion of the outermost layer without the convex part is preferably 1 nm or more, more preferably 10 nm or more, preferably 500 nm or less, more preferably 100 nm or less.
  • the coating with the metal part of the outermost layer can be made uniform, the corrosion resistance is sufficiently high, and the connection resistance between the electrodes is sufficiently high Lower. Further, when the outermost layer is more expensive than the metal part of the inner layer, the thinner the outermost layer, the lower the cost.
  • the thickness of the metal part can be measured by observing the cross section of the metal-containing particles using, for example, a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the metal-containing particles include a plurality of core substances that protrude the surface of the metal part, and the metal part is formed so as to form the plurality of protrusions or the plurality of protrusions in the metal part. It is more preferable to provide a plurality of core materials that are raised on the surface. Since the core substance is embedded in the metal part, it is easy for the metal part to have a plurality of protrusions or protrusions on the outer surface. However, in order to form convex portions or protrusions on the outer surfaces of the metal-containing particles and the metal portion, the core substance is not necessarily used.
  • metal nuclei are generated by electroless plating, and metal nuclei are attached to the surface of the substrate particles or metal parts, and further electroless Examples include a method of forming a metal part by plating.
  • a method of forming a metal part by electroless plating after attaching a core substance to the surface of the base particle, and a metal part by electroless plating on the surface of the base particle a method of forming a metal part by electroless plating after the core material is attached.
  • the core substance is added to the dispersion of the base particle, and the core substance is applied to the surface of the base particle, for example, van der Waals force.
  • the method of making a core substance accumulate and adhere on the surface of the base particle in a dispersion liquid is preferable.
  • the metal part it is easy for the metal part to have a plurality of protrusions or a plurality of protrusions on the outer surface by embedding the core substance in the metal part.
  • the core substance is not necessarily used.
  • a method of forming a metal part by electroless plating after attaching a core substance to the surface of the base particle a method of forming a metal part by electroless plating on the surface of the base particle.
  • the method include forming a metal part by electroless plating after the core material has been formed, and adding a core substance in the middle of forming the metal part by electroless plating on the surface of the substrate particles. It is done.
  • the material of the core substance includes a conductive substance and a non-conductive substance.
  • the conductive material include conductive non-metals such as metals, metal oxides, and graphite, and conductive polymers.
  • the conductive polymer include polyacetylene.
  • the non-conductive substance include silica, alumina, barium titanate, zirconia, and the like. Among them, metal is preferable because conductivity can be increased and connection resistance can be effectively reduced.
  • the core substance is preferably metal particles. As the metal that is the material of the core substance, the metals mentioned as the material of the conductive material can be used as appropriate.
  • the core material include barium titanate (Mohs hardness 4.5), nickel (Mohs hardness 5), silica (silicon dioxide, Mohs hardness 6-7), titanium oxide (Mohs hardness 7), zirconia. (Mohs hardness 8-9), alumina (Mohs hardness 9), tungsten carbide (Mohs hardness 9), diamond (Mohs hardness 10), and the like.
  • the inorganic particles are preferably nickel, silica, titanium oxide, zirconia, alumina, tungsten carbide or diamond, more preferably silica, titanium oxide, zirconia, alumina, tungsten carbide or diamond, titanium oxide, zirconia.
  • Alumina, tungsten carbide or diamond is more preferable, and zirconia, alumina, tungsten carbide or diamond is particularly preferable.
  • the Mohs hardness of the core material is preferably 5 or more, more preferably 6 or more, still more preferably 7 or more, and particularly preferably 7.5 or more.
  • the shape of the core substance is not particularly limited.
  • the shape of the core substance is preferably a lump.
  • Examples of the core substance include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.
  • the average diameter (average particle diameter) of the core substance is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 0.9 ⁇ m or less, more preferably 0.2 ⁇ m or less.
  • the connection resistance between the electrodes is effectively reduced.
  • the “average diameter (average particle diameter)” of the core substance indicates a number average diameter (number average particle diameter).
  • the average diameter of the core material is obtained by observing 50 arbitrary core materials with an electron microscope or an optical microscope and calculating an average value.
  • the metal-containing particle according to the present invention includes an insulating substance disposed on the outer surface of the metal part.
  • an insulating substance disposed on the outer surface of the metal part.
  • the metal-containing particles when used for connection between the electrodes, a short circuit between adjacent electrodes can be prevented.
  • an insulating substance is present between the plurality of electrodes, so that a short circuit between electrodes adjacent in the lateral direction can be prevented instead of between the upper and lower electrodes.
  • the insulating substance between the metal part of a metal containing particle and an electrode can be easily excluded by pressurizing a metal containing particle with two electrodes in the case of the connection between electrodes.
  • the metal part Since the metal part has a plurality of protrusions on the outer surface, the insulating substance between the metal part of the metal-containing particles and the electrode can be easily excluded. Moreover, when a metal part has a some convex part on an outer surface, the insulating substance between the metal part of a metal containing particle and an electrode can be excluded easily.
  • the insulating substance is preferably an insulating particle because the insulating substance can be more easily removed during crimping between the electrodes.
  • Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer.
  • Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate.
  • Examples of the block polymer include polystyrene, styrene-acrylate copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, and hydrogenated products thereof.
  • Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers.
  • thermosetting resin an epoxy resin, a phenol resin, a melamine resin, etc.
  • water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose. Of these, water-soluble resins are preferable, and polyvinyl alcohol is more preferable.
  • a method of disposing an insulating material on the surface of the metal part there are a chemical method, a physical or mechanical method, and the like.
  • the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method.
  • the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spraying, dipping, and vacuum deposition. Especially, since the insulating substance is difficult to be detached, a method of arranging the insulating substance on the surface of the metal part through a chemical bond is preferable.
  • the outer surface of the metal part and the surface of an insulating substance may each be coated with a compound having a reactive functional group.
  • the outer surface of the metal part and the surface of the insulating substance may not be directly chemically bonded, but may be indirectly chemically bonded by a compound having a reactive functional group.
  • the carboxyl group may be chemically bonded to a functional group on the surface of the insulating substance via a polymer electrolyte such as polyethyleneimine.
  • the average diameter (average particle diameter) of the insulating material can be appropriately selected depending on the particle diameter of the metal-containing particles and the use of the metal-containing particles.
  • the average diameter (average particle diameter) of the insulating substance is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less.
  • the average diameter of the insulating material is equal to or more than the above lower limit, when the metal-containing particles are dispersed in the binder resin, the metal parts in the plurality of metal-containing particles are difficult to contact each other.
  • the average diameter of the insulating material is not more than the above upper limit, it is not necessary to make the pressure too high in order to eliminate the insulating material between the electrode and the metal-containing particles at the time of connection between the electrodes. There is no need for heating.
  • the “average diameter (average particle diameter)” of the insulating material indicates a number average diameter (number average particle diameter).
  • the average diameter of the insulating material is determined using a particle size distribution measuring device or the like.
  • the metal-containing particles according to the present invention can form a particle-connected body as shown in FIG. 15 by melting the protrusions of the metal part and then solidifying.
  • grain coupling body is useful as a novel material which can improve connection reliability higher than the conventional metal containing particle
  • a particle connected body in which a plurality of metal-containing particles also referred to as a metal-containing particle main body as distinguished from the metal-containing particles according to the present invention
  • a metal-containing particle main body as distinguished from the metal-containing particles according to the present invention
  • the metal-containing particles and the columnar connecting portions constituting the particle-linked body are formed by melting and solidifying the protrusions of the metal-containing particles according to the present invention. Particle connected body.
  • the particle linked body of the present invention can be produced by the method described above, but the production method is not limited to the method described above.
  • the metal-containing particles and the columnar bodies may be manufactured separately, and the metal-containing particles may be connected by the columnar bodies to form the columnar connecting portions.
  • the columnar connecting portion may be a columnar connecting portion or a polygonal columnar connecting portion, and the central portion of the column may be thicker or thinner.
  • the diameter (d) of the circumscribed circle of the connection surface with the metal-containing particles is preferably 3 nm or more, more preferably 100 nm or more, preferably 10,000 nm or less, more preferably 1000 nm or less.
  • the length (l) of the columnar connecting portion is preferably 3 nm or more, more preferably 100 nm or more, preferably 10,000 nm or less, more preferably 1000 nm or less.
  • the ratio ((d) / (l)) of the length (l) of the columnar connecting portion to the diameter (d) of the circumscribed circle of the connection surface with the metal-containing particles is preferably 0.001. As mentioned above, More preferably, it is 0.1 or more, Preferably it is 100 or less, More preferably, it is 10 or less.
  • the particle linked body of the present invention may be a linked body of two metal-containing particles as shown in FIG. 15 or a linked body of three or more metal-containing particles.
  • connection material The connection material according to the present invention is suitably used for forming a connection portion that connects two connection target members.
  • the connection material includes the metal-containing particles described above and a resin. It is preferable that the connection material is used for forming the connection portion by melting the tips of the protrusions of the metal portion of the plurality of metal-containing particles and then solidifying.
  • the resin is not particularly limited.
  • the resin is a binder that disperses the metal-containing particles.
  • the resin preferably includes a thermoplastic resin or a curable resin, and more preferably includes a curable resin.
  • the curable resin include a photocurable resin and a thermosetting resin.
  • the photocurable resin preferably contains a photocurable resin and a photopolymerization initiator.
  • the thermosetting resin preferably contains a thermosetting resin and a thermosetting agent.
  • the resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for the said resin, only 1 type may be used and 2 or more types may be used together.
  • Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin.
  • examples of the thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin.
  • examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin.
  • the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin.
  • thermoplastic block copolymer examples include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogenated products of styrene block copolymers.
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • a reducing agent is used when the protrusion of the metal part contains a metal oxide.
  • the reducing agent include alcohol compounds (compounds having an alcoholic hydroxyl group), carboxylic acid compounds (compounds having a carboxy group), amine compounds (compounds having an amino group), and the like.
  • the said reducing agent only 1 type may be used and 2 or more types may be used together.
  • the alcohol compound examples include alkyl alcohols. Specific examples of the alcohol compound include, for example, ethanol, propanol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol. , Pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol and icosyl alcohol.
  • the alcohol compound is not limited to a primary alcohol type compound, but a secondary alcohol type compound, a tertiary alcohol type compound, an alkanediol, and an alcohol compound having a cyclic structure can also be used. Furthermore, as the alcohol compound, a compound having a large number of alcohol groups such as ethylene glycol and triethylene glycol may be used. Moreover, you may use compounds, such as a citric acid, ascorbic acid, and glucose, as said alcohol compound.
  • Examples of the carboxylic acid compound include alkyl carboxylic acids.
  • Specific examples of the carboxylic acid compound include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid.
  • Examples include acids, octadecanoic acid, nonadecanoic acid and icosanoic acid.
  • the carboxylic acid compound is not limited to a primary carboxylic acid type compound, and a secondary carboxylic acid type compound, a tertiary carboxylic acid type compound, a dicarboxylic acid, and a carboxyl compound having a cyclic structure can also be used.
  • Examples of the amine compound include alkylamines. Specific examples of the amine compound include butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, Examples include heptadecylamine, octadecylamine, nonadecylamine and icodecylamine.
  • the amine compound may have a branched structure.
  • Examples of the amine compound having a branched structure include 2-ethylhexylamine and 1,5-dimethylhexylamine.
  • the amine compound is not limited to a primary amine type compound, and a secondary amine type compound, a tertiary amine type compound, and an amine compound having a cyclic structure can also be used.
  • the reducing agent may be an organic substance having an aldehyde group, an ester group, a sulfonyl group, or a ketone group, or an organic substance such as a carboxylic acid metal salt. While the carboxylic acid metal salt is used as a precursor of metal particles, it also contains an organic substance, so that it is also used as a reducing agent for metal oxide particles.
  • connection material is, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer.
  • various additives such as ultraviolet absorbers, lubricants, antistatic agents and flame retardants may be contained.
  • connection material is preferably used for conductive connection, and is preferably a conductive connection material.
  • the connection material is preferably used for anisotropic conductive connection, and is preferably an anisotropic conductive connection material.
  • the connecting material can be used as a paste and a film. When the connection material is a film, a film containing no metal-containing particles may be laminated on a film containing metal-containing particles.
  • the paste is preferably a conductive paste, and more preferably an anisotropic conductive paste.
  • the film is preferably a conductive film, and more preferably an anisotropic conductive film.
  • the content of the resin is preferably 1% by weight or more, more preferably 5% by weight or more, 10% by weight or more, or 30% by weight or more. It may be 70% by weight or more, preferably 99.99% by weight or less, more preferably 99.9% by weight or less.
  • the content of the resin is not less than the above lower limit and not more than the above upper limit, connection reliability is further enhanced.
  • the content of the metal-containing particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 99% by weight or less, more preferably 95% by weight.
  • it may be 80% by weight or less, 60% by weight or less, 40% by weight or less, 20% by weight or less, or 10% by weight or less. Good.
  • connection reliability is further enhanced.
  • the metal-containing particles when the content of the metal-containing particles is not less than the lower limit and not more than the upper limit, the metal-containing particles can be sufficiently present between the first and second connection target members, It can further suppress that the space
  • connection material may contain metal atom-containing particles that do not have base material particles separately from the metal-containing particles.
  • the metal atom-containing particles include metal particles and metal compound particles.
  • the metal compound particle includes a metal atom and an atom other than the metal atom.
  • Specific examples of the metal compound particles include metal oxide particles, metal carbonate particles, metal carboxylate particles, and metal complex particles.
  • the metal compound particles are preferably metal oxide particles.
  • the metal oxide particles are sintered after becoming metal particles by heating at the time of connection in the presence of a reducing agent.
  • the metal oxide particles are metal particle precursors.
  • the metal carboxylate particles include metal acetate particles.
  • the metal constituting the metal particles and the metal oxide particles examples include silver, copper, nickel, and gold. Silver or copper is preferred, and silver is particularly preferred. Therefore, the metal particles are preferably silver particles or copper particles, and more preferably silver particles.
  • the metal oxide particles are preferably silver oxide particles or copper oxide particles, and more preferably silver oxide particles. When silver particles and silver oxide particles are used, there are few residues after connection and the volume reduction rate is very small. Examples of the silver oxide in the silver oxide particles include Ag 2 O and AgO.
  • the metal atom-containing particles are preferably sintered by heating at less than 400 ° C.
  • the temperature at which the metal atom-containing particles are sintered (sintering temperature) is more preferably 350 ° C. or lower, and preferably 300 ° C. or higher.
  • sintering temperature is more preferably 350 ° C. or lower, and preferably 300 ° C. or higher.
  • connection material containing the metal atom-containing particles is a connection material containing metal particles having an average particle diameter of 1 nm or more and 100 nm or less, or reduced with metal oxide particles having an average particle diameter of 1 nm or more and 50 ⁇ m or less. It is preferable that it is a connection material containing an agent. When such a connection material is used, the metal atom-containing particles can be satisfactorily sintered by heating during connection.
  • the average particle diameter of the metal oxide particles is preferably 5 ⁇ m or less.
  • the particle diameter of the metal atom-containing particles indicates the diameter when the metal atom-containing particles are spherical, and indicates the maximum diameter when the metal atom-containing particles are not true spherical.
  • the content of the metal atom-containing particles is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and 100% by weight or less, preferably 99%. % By weight or less, more preferably 90% by weight or less.
  • the total amount of the connecting material may be the metal atom-containing particles.
  • a reducing agent is used when the metal atom-containing particles are metal oxide particles.
  • the reducing agent include alcohol compounds (compounds having an alcoholic hydroxyl group), carboxylic acid compounds (compounds having a carboxy group), amine compounds (compounds having an amino group), and the like.
  • the said reducing agent only 1 type may be used and 2 or more types may be used together.
  • the alcohol compound examples include alkyl alcohols. Specific examples of the alcohol compound include, for example, ethanol, propanol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol. , Pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol and icosyl alcohol.
  • the alcohol compound is not limited to a primary alcohol type compound, but a secondary alcohol type compound, a tertiary alcohol type compound, an alkanediol, and an alcohol compound having a cyclic structure can also be used. Furthermore, as the alcohol compound, a compound having a large number of alcohol groups such as ethylene glycol and triethylene glycol may be used. Moreover, you may use compounds, such as a citric acid, ascorbic acid, and glucose, as said alcohol compound.
  • Examples of the carboxylic acid compound include alkyl carboxylic acids.
  • Specific examples of the carboxylic acid compound include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid.
  • Examples include acids, octadecanoic acid, nonadecanoic acid and icosanoic acid.
  • the carboxylic acid compound is not limited to a primary carboxylic acid type compound, and a secondary carboxylic acid type compound, a tertiary carboxylic acid type compound, a dicarboxylic acid, and a carboxyl compound having a cyclic structure can also be used.
  • Examples of the amine compound include alkylamines. Specific examples of the amine compound include butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, Examples include heptadecylamine, octadecylamine, nonadecylamine and icodecylamine.
  • the amine compound may have a branched structure.
  • Examples of the amine compound having a branched structure include 2-ethylhexylamine and 1,5-dimethylhexylamine.
  • the amine compound is not limited to a primary amine type compound, and a secondary amine type compound, a tertiary amine type compound, and an amine compound having a cyclic structure can also be used.
  • the reducing agent may be an organic substance having an aldehyde group, an ester group, a sulfonyl group or a ketone group, or an organic substance such as a carboxylic acid metal salt. While the carboxylic acid metal salt is used as a precursor of metal particles, it also contains an organic substance, so that it is also used as a reducing agent for metal oxide particles.
  • the reducing agent tends to aggregate at the time of joining and voids are likely to occur at the joint.
  • the carboxylic acid metal salt By using the carboxylic acid metal salt, the carboxylic acid metal salt is not melted by heating at the time of joining, so that the generation of voids can be suppressed.
  • a metal compound containing an organic substance may be used as the reducing agent.
  • the content of the reducing agent in 100% by weight of the connecting material is preferably 1% by weight or more, more preferably 10% by weight or more, and preferably 90% by weight or less. More preferably, it is 70 weight% or less, More preferably, it is 50 weight% or less.
  • the content of the reducing agent is not less than the above lower limit, the metal atom-containing particles can be sintered more densely. As a result, heat dissipation and heat resistance at the joint are also increased.
  • the content of the metal oxide particles is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 60% by weight or more, and preferably 99.99% by weight or less. More preferably, it is 99.9% by weight or less, still more preferably 99.5% by weight or less, still more preferably 99% by weight or less, particularly preferably 90% by weight or less, and most preferably 80% by weight or less.
  • the binder used for the paste is not particularly limited.
  • the binder preferably disappears when the metal atom-containing particles are sintered.
  • the said binder only 1 type may be used and 2 or more types may be used together.
  • binder examples include aliphatic solvents, ketone solvents, aromatic solvents, ester solvents, ether solvents, alcohol solvents, paraffin solvents, petroleum solvents, and the like.
  • Examples of the aliphatic solvent include cyclohexane, methylcyclohexane, and ethylcyclohexane.
  • Examples of the ketone solvent include acetone and methyl ethyl ketone.
  • Examples of the aromatic solvent include toluene and xylene.
  • Examples of the ester solvent include ethyl acetate, butyl acetate and isopropyl acetate.
  • Examples of the ether solvent include tetrahydrofuran (THF) and dioxane.
  • Examples of the alcohol solvent include ethanol and butanol.
  • Examples of the paraffinic solvent include paraffin oil and naphthenic oil.
  • Examples of the petroleum solvent include mineral terpenes and naphtha.
  • connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first and second connection target members.
  • connection portion is formed of the metal-containing particles or the connection material.
  • the material of the connection part is the metal-containing particle or the connection material.
  • the method for manufacturing a connection structure includes the step of arranging the metal-containing particles or the connection material between the first connection target member and the second connection target member.
  • the metal-containing particles are heated to melt the tips of the protrusions of the metal part, solidify after melting, and the first connection target member and the second connection are formed by the metal-containing particles or the connection material. Forming a connection portion connecting the target member.
  • FIG. 9 is a cross-sectional view schematically showing a connection structure using metal-containing particles according to the first embodiment of the present invention.
  • a connection structure 51 shown in FIG. 9 includes a first connection target member 52, a second connection target member 53, and a connection portion 54 connecting the first and second connection target members 52 and 53.
  • Connection portion 54 includes metal-containing particles 1 and a resin (such as a cured resin).
  • the connection part 54 is formed of a connection material including the metal-containing particles 1.
  • the material of the connection part 54 is the connection material.
  • the connection portion 54 is preferably formed by curing a connection material.
  • grains 1 is solidified after fuse
  • the connection part 54 includes a joined body of a plurality of metal-containing particles 1. In the connection structure 51, the metal-containing particles 1 and the first connection target member 51 are joined, and the metal-containing particles 1 and the second connection target member 53 are joined.
  • metal-containing particles 1A, 1B, 1C, 1D, 1E, 1F, and 1G may be used.
  • the first connection target member 52 has a plurality of first electrodes 52a on the surface (upper surface).
  • the second connection target member 53 has a plurality of second electrodes 53a on the surface (lower surface).
  • the first electrode 52 a and the second electrode 53 a are electrically connected by one or more metal-containing particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the metal-containing particles 1.
  • the metal-containing particle 1 and the first electrode 52a are joined, and the metal-containing particle 1 and the second electrode 53a are joined.
  • connection material is disposed between the first connection target member and the second connection target member to obtain a laminate, and then the laminate is heated and pressurized. Methods and the like.
  • the pressurizing pressure is about 9.8 ⁇ 10 4 to 4.9 ⁇ 10 6 Pa.
  • the heating temperature is about 120 to 220 ° C.
  • connection target member examples include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components that are circuit boards such as printed boards, flexible printed boards, glass epoxy boards, and glass boards.
  • the connection target member is preferably an electronic component.
  • the metal-containing particles are preferably used for electrical connection of electrodes in an electronic component.
  • the electrode provided on the connection target member examples include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a SUS electrode, a molybdenum electrode, and a tungsten electrode.
  • the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode.
  • the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode.
  • the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated
  • the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element.
  • the trivalent metal element include Sn, Al, and Ga.
  • FIG. 10 is a cross-sectional view schematically showing a modification of the connection structure using the metal-containing particles according to the first embodiment of the present invention.
  • connection structure 61 shown in FIG. 10 connects the first connection target member 62, the second connection target members 63 and 64, and the first connection target member 62 and the second connection target members 63 and 64.
  • Connection portions 65 and 66 are formed using a connection material including metal-containing particles 1 and other metal-containing particles 67.
  • the material of the connection parts 65 and 66 is the connection material.
  • connection portion 65 and the second connection target member 63 are arranged on the first surface (one surface) side of the first connection target member 62.
  • the connection part 65 connects the first connection target member 62 and the second connection target member 63.
  • connection part 66 and the second connection target member 64 are arranged on the second surface (the other surface) side opposite to the first surface of the first connection target member 62.
  • the connection part 66 connects the first connection target member 62 and the second connection target member 64.
  • the metal-containing particles 1 and the metal-containing particles 67 are arranged between the first connection target member 62 and the second connection target members 63 and 64, respectively.
  • the metal atom-containing particles and the metal-containing particles 1 are in a sintered sintered state.
  • the metal-containing particles 1 are arranged between the first connection target member 62 and the second connection target members 63 and 64.
  • the first connection target member 62 and the second connection target members 63 and 64 are connected by the metal-containing particles 1.
  • connection structure 61 includes the heat sink 68, the second connection target member 63, the connection portion 65, the first connection target member 62, the connection portion 66, the second connection target member 64, and the heat sink 69 stacked in this order. It has the part which was made.
  • connection target member 62 a power semiconductor element made of Si, SiC, GaN or the like used for a rectifier diode, a power transistor (power MOSFET, insulated gate bipolar transistor), a thyristor, a gate turn-off thyristor, a triac, etc. Is mentioned.
  • a large amount of heat is likely to be generated in the first connection target member 62 when the connection structure 61 is used. Therefore, it is necessary to efficiently dissipate the heat generated from the first connection target member 62 to the heat sinks 68 and 69. For this reason, the connection portions 65 and 66 disposed between the first connection target member 62 and the heat sinks 68 and 69 are required to have high heat dissipation and high reliability.
  • Examples of the second connection target members 63 and 64 include a substrate made of ceramic, plastic, or the like.
  • the connecting portions 65 and 66 are formed by heating the connecting material to melt the tips of the metal-containing particles and then solidifying them.
  • grain coupling body and connection material of this invention can also be applied to the member for conduction
  • an aspect of the continuity inspection member will be described.
  • the member for continuity inspection is not limited to the following aspect.
  • the continuity inspection member and the continuity member may be sheet-like continuity members.
  • FIG. 19 (a) and 19 (b) are a plan view and a cross-sectional view showing an example of a continuity test member.
  • FIG. 19B is a cross-sectional view taken along the line AA in FIG.
  • 19 (a) and 19 (b) includes a base 12 having a through hole 12a and a conductive portion 13 disposed in the through hole 12a of the base 12.
  • the material of the conductive part 13 includes the metal-containing particles.
  • the continuity inspection member 11 may be a continuity member.
  • the base is a member that becomes a substrate of the continuity testing member.
  • the substrate preferably has an insulating property, and the substrate is preferably formed of an insulating material.
  • An example of the insulating material is an insulating resin.
  • the insulating resin constituting the substrate may be, for example, either a thermoplastic resin or a thermosetting resin.
  • the thermoplastic resin include polyester resin, polystyrene resin, polyethylene resin, polyamide resin, ABS resin, and polycarbonate resin.
  • the thermosetting resin include epoxy resin, urethane resin, polyimide resin, polyether ether ketone resin, polyamide imide resin, polyether imide resin, silicone resin, and phenol resin.
  • the silicone resin include silicone rubber.
  • the base is formed of an insulating resin
  • only one type of insulating resin constituting the base may be used, or two or more types may be used in combination.
  • the base is, for example, a plate shape or a sheet shape.
  • the sheet form includes a film form.
  • the thickness of the substrate can be appropriately set according to the type of the continuity test member, and may be, for example, 0.005 mm or more and 50 mm or less.
  • the size of the substrate in plan view can also be set appropriately according to the target inspection apparatus.
  • the base can be obtained, for example, by molding an insulating material such as the insulating resin as a raw material into a desired shape.
  • a plurality of the through holes of the base body are arranged on the base body. It is preferable that the through hole penetrates in the thickness direction of the substrate.
  • the through hole of the base body may be formed in a columnar shape, but is not limited to a columnar shape, and may be formed in other shapes, for example, a polygonal column shape. Further, the through hole may be formed in a tapered shape that tapers in one direction, or may be formed in a distorted shape.
  • the size of the through hole for example, the apparent area of the through hole in plan view, can be formed to an appropriate size, for example, formed to a size that can accommodate and hold the conductive portion. Just do it. If the through hole is, for example, a cylindrical shape, the diameter of the through hole is preferably 0.01 mm or more, and preferably 10 mm or less.
  • all of the through holes of the base body may have the same shape and the same size, or a part of the through holes of the base body may have a different shape or size from other through holes. .
  • the number of the through holes of the base body can be set within an appropriate range as long as the number of the through holes can be inspected, and can be appropriately set according to a target inspection apparatus.
  • the location of the through hole of the base can also be set as appropriate according to the target inspection apparatus.
  • the method for forming the through hole of the substrate is not particularly limited, and the through hole can be formed by a known method (for example, laser processing).
  • the conductive part in the through hole of the base has conductivity.
  • the conductive part includes particles derived from the metal-containing particles.
  • the conductive part is formed by accommodating a plurality of metal-containing particles in a through hole.
  • the conductive part includes an aggregate (particle group) of particles derived from metal-containing particles.
  • the material for the conductive part may include materials other than the metal-containing particles.
  • the material of the conductive part can contain a binder in addition to the metal-containing particles.
  • the metal-containing particles are more firmly aggregated, whereby the particles derived from the metal-containing particles are easily held in the through holes.
  • the binder is not particularly limited, and examples thereof include a photocurable resin and a thermosetting resin.
  • the photocurable resin preferably contains a photocurable resin and a photopolymerization initiator.
  • the thermosetting resin preferably contains a thermosetting resin and a thermosetting agent.
  • the resin include silicone copolymers, vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for the said resin, only 1 type may be used and 2 or more types may be used together.
  • the particles derived from the metal-containing particles are preferably closely packed in the through holes. In this case, a more reliable continuity test can be performed by the continuity test member. It is preferable that the conductive portion is accommodated in the through-hole so as to be conductive across the front and back surfaces of the conductive inspection member or the conductive member.
  • the particles derived from the metal-containing particles are continuously present from the surface to the back surface of the conductive part while the particles derived from the metal-containing particles are in contact with each other. In this case, the conductivity of the conductive part is improved.
  • the method for accommodating the conductive part in the through hole is not particularly limited.
  • the conductive part is formed in the through-hole by filling the metal-containing particle in the through hole by a method of applying the material containing the metal-containing particle and the binder to the substrate, and curing it under appropriate conditions. Can do.
  • an electroconductive part is accommodated in a through-hole.
  • the material containing the metal-containing particles and the binder may contain a solvent as necessary.
  • the material containing the metal-containing particles and the binder is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, preferably 10 parts by weight or more, preferably 100 parts by weight of the metal-containing particles in terms of solid content. 70 parts by weight or less, more preferably 50 parts by weight or less.
  • the above continuity test member can be used as a probe card.
  • the continuity test member may include other components as long as the effects of the present invention are not impaired.
  • 20 (a) to 20 (c) are diagrams schematically showing a state in which the electrical characteristics of the electronic circuit device are inspected by the continuity inspection member.
  • the electronic circuit device is a BGA substrate 31 (ball grid array substrate).
  • the BGA substrate 31 is a substrate having a structure in which connection pads are arranged on a multilayer substrate 31A in a lattice shape, and solder balls 31B are arranged on each pad.
  • the continuity test member 21 is a probe card.
  • a plurality of through holes 22a are formed in a base 22, and a conductive portion 23 is accommodated in the through hole 22a.
  • a BGA substrate 31 and a continuity test member 21 are prepared as shown in FIG. 20A, and the BGA substrate 31 is brought into contact with the continuity test member 21 and compressed as shown in FIG. At this time, the solder ball 31B contacts the conductive portion 23 in the through hole 22a.
  • the ammeter 32 can be connected and a continuity test can be performed to determine whether the BGA substrate 31 is acceptable.
  • Example 1 As the base particle A, divinylbenzene copolymer resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared.
  • divinylbenzene copolymer resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared.
  • the base particle A After 10 parts by weight of the base particle A was dispersed in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, the base particle A was taken out by filtering the solution. Subsequently, the base particle A was added to 100 parts by weight of a 1% by weight dimethylamine borane solution to activate the surface of the base particle A. Suspension (A) was obtained by fully washing the base particle A whose surface was activated, and then adding and dispersing in 500 parts by weight of distilled water.
  • Suspension (B) was put into a solution containing 20 g / L of copper sulfate and 30 g / L of ethylenediaminetetraacetic acid to obtain a particle mixture (C).
  • an electroless copper plating solution a mixed solution containing 250 g / L of copper sulfate, 150 g / L of ethylenediaminetetraacetic acid, 100 g / L of sodium gluconate, and 50 g / L of formaldehyde is adjusted to pH 10.5 with ammonia.
  • a plating solution (D) was prepared.
  • a silver plating solution (E) prepared by adjusting a mixed solution containing 30 g / L of silver nitrate, 100 g / L of succinimide and 20 g / L of formaldehyde to pH 8.0 with aqueous ammonia is prepared. did.
  • a plating solution for forming a protrusion (F) (pH 10.0) containing dimethylamine borane 100 g / L and sodium hydroxide 0.5 g / L was prepared.
  • the copper plating solution (D) was gradually added dropwise to the dispersed particle mixture (C) adjusted to 55 ° C. to perform electroless copper plating.
  • the dropping rate of the copper plating solution (D) was 30 mL / min, the dropping time was 30 minutes, and electroless copper plating was performed.
  • the copper metal part was arrange
  • the particles are taken out and washed with water, whereby a copper metal part is disposed on the surface of the base particle A and a metal part having a convex part on the surface. Obtained particles.
  • the particles were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a particle mixture (H).
  • the silver plating solution (E) was gradually added dropwise to the dispersed particle mixture (H) adjusted to 60 ° C. to perform electroless silver plating.
  • the dropping rate of the silver plating solution (E) was 10 mL / min, the dropping time was 30 minutes, and electroless silver plating was performed.
  • the protrusion forming plating solution (F) was gradually dropped to form protrusions. Protrusion formation was performed at a dropping rate of the plating solution for forming protrusions (F) of 1 mL / min and a dropping time of 10 minutes.
  • the protrusion forming plating solution (F) silver plating was performed while dispersing the generated silver protrusion nuclei by ultrasonic stirring (protrusion forming step). Thereafter, the particles are taken out by filtration, washed with water, and dried, so that copper and silver metal parts (thickness of the whole metal part in the part having no convex part: 0.1 ⁇ m) are arranged on the surface of the base particle A.
  • grains provided with the metal part which has a convex part on the surface and has a some protrusion on the surface of a convex part were obtained.
  • Example 2 Metal-containing particles were obtained in the same manner as in Example 1 except that the metal nickel particle slurry was changed to alumina particle slurry (average particle diameter 150 nm).
  • Example 3 The suspension (A) obtained in Example 1 was put into a solution containing nickel sulfate 40 ppm, trisodium citrate 2 g / L, and aqueous ammonia 10 g / L to obtain a particle mixture (B).
  • a plating solution (C) for forming needle-like protrusions which is an electroless copper-nickel-phosphorus alloy plating solution obtained by adjusting a mixed solution containing polyethylene glycol 1000 (molecular weight: 1000) 5 mg / L to pH 10.0 with ammonia water. Prepared.
  • a silver plating solution (D) prepared by adjusting a mixed solution of silver nitrate 30 g / L, succinimide 100 g / L, and formaldehyde 20 g / L to pH 8.0 with aqueous ammonia was prepared. .
  • a plating solution for forming a protrusion (E) (pH 10.0) containing dimethylamine borane 100 g / L and sodium hydroxide 0.5 g / L was prepared.
  • the needle-like projection forming plating solution (C) was gradually dropped into the dispersed particle mixture (B) adjusted to 70 ° C. to form needle-like projections.
  • the electroless copper-nickel-phosphorus alloy plating was carried out at a dropping rate of the needle-like projection forming plating solution (C) of 40 mL / min and a dropping time of 60 minutes (acicular projection-forming and copper-nickel-phosphorus alloy plating). Process). Thereafter, the particles were taken out by filtration to obtain particles (F) having a metal part with a copper-nickel-phosphorus alloy metal part disposed on the surface of the base particle A and having a convex part on the surface. The particles (F) were added to 500 parts by weight of distilled water and dispersed to obtain a suspension (G).
  • the particles are taken out and washed with water, so that the copper-nickel-phosphorus alloy metal part is arranged on the surface of the base particle A, and the surface is acicular.
  • grains provided with the metal part which has a convex part were obtained.
  • the particles were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a particle mixture (H).
  • the silver plating solution (D) was gradually dropped into the dispersed particle mixture (H) adjusted to 60 ° C. to perform electroless silver plating.
  • the dropping rate of the silver plating solution (D) was 10 mL / min, the dropping time was 30 minutes, and electroless silver plating was performed.
  • the protrusion forming plating solution (E) was gradually dropped to form protrusions.
  • the protrusion formation was performed at a dropping rate of the plating solution for forming protrusions (E) of 1 mL / min and a dropping time of 10 minutes.
  • silver plating was performed while dispersing the generated silver projection nuclei by ultrasonic stirring (projection formation step).
  • the particles are taken out by filtration, washed with water, and dried to obtain a copper-nickel-phosphorus alloy and a silver metal part on the surface of the base particle A (total thickness of the metal part in the part having no projection: 0 0.1 ⁇ m) was obtained, and metal-containing particles having a plurality of needle-like protrusions on the surface and a metal part having a plurality of protrusions on the surface of the protrusion were obtained.
  • Example 4 The suspension (A) obtained in Example 1 was put into a solution containing 80 g / L of nickel sulfate, 10 ppm of thallium nitrate, and 5 ppm of bismuth nitrate to obtain a particle mixture (B).
  • a plating solution (C) for forming needle-like protrusions which is an electroless high-purity nickel plating solution adjusted to pH 9.0 with sodium hydroxide, was prepared.
  • a silver plating solution (D) prepared by adjusting a mixed solution containing silver nitrate 30 g / L, succinimide 100 g / L, and formaldehyde 20 g / L to pH 8.0 with aqueous ammonia is prepared. did.
  • a plating solution for forming a protrusion (E) (pH 10.0) containing dimethylamine borane 100 g / L and sodium hydroxide 0.5 g / L was prepared.
  • the needle-like projection forming plating solution (C) was gradually dropped into the dispersed particle mixture (B) adjusted to 60 ° C. to form needle-like projections.
  • Electrolytic high-purity nickel plating was carried out at a dropping rate of the needle-like protrusion-forming plating solution (C) of 20 mL / min and a dropping time of 50 minutes (needle-like protrusion formation and copper-nickel-phosphorus alloy plating step). Thereafter, the particles were taken out by filtration to obtain particles (F) having a high purity nickel metal part disposed on the surface of the base particle A and having a metal part having a convex part on the surface. The particles (F) were added to 500 parts by weight of distilled water and dispersed to obtain a suspension (G).
  • the particles are taken out and washed, whereby a high-purity nickel metal part is disposed on the surface of the base particle A and has a needle-like convex part on the surface. Particles with a metal part were obtained.
  • the particles were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a particle mixture (H).
  • the silver plating solution (D) was gradually dropped into the dispersed particle mixture (H) adjusted to 60 ° C. to perform electroless silver plating.
  • the dropping rate of the silver plating solution (D) was 10 mL / min, the dropping time was 30 minutes, and electroless silver plating was performed.
  • the protrusion forming plating solution (E) was gradually dropped to form protrusions.
  • the protrusion formation was performed at a dropping rate of the plating solution for forming protrusions (E) of 1 mL / min and a dropping time of 10 minutes.
  • silver plating was performed while dispersing the generated silver projection nuclei by ultrasonic stirring (projection formation step).
  • the particles are taken out by filtration, and high-purity nickel and silver metal parts are arranged on the surface of the base particle A, and have a needle-like convex part on the surface, and a plurality of protrusions on the surface of the convex part A particle mixed liquid (I) having a metal part having the following was obtained.
  • the particles are taken out, washed with water, and dried to obtain high-purity nickel and silver metal parts on the surface of the base particle A (the metal part in the part having no protrusions).
  • Total thickness: 0.1 ⁇ m) was arranged, and metal-containing particles having a plurality of needle-like protrusions on the surface and a metal part having a plurality of protrusions on the surface of the protrusions were obtained.
  • Example 5 The suspension (A) obtained in Example 1 was put in a solution containing 500 ppm of silver nitrate, 10 g / L of succinimide, and 10 g / L of aqueous ammonia to obtain a particle mixture (B).
  • a silver plating solution (C) was prepared by adjusting a mixed solution containing 30 g / L of silver nitrate, 100 g / L of succinimide, and 20 g / L of formaldehyde to pH 8 with aqueous ammonia.
  • a plating solution (D) (pH 10.0) for protrusion formation containing dimethylamine borane 100 g / L and sodium hydroxide 0.5 g / L was prepared.
  • the electroless silver plating solution (C) was gradually added dropwise to the dispersed particle mixture (B) adjusted to 60 ° C. to form needle-like protrusions.
  • the electroless silver plating solution (C) was dropped at a rate of 10 mL / min and a dropping time was 30 minutes (electroless silver plating step).
  • the protrusion forming plating solution (D) was gradually dropped to form protrusions.
  • the protrusion formation was carried out at a dropping rate of the plating solution for protrusion formation (D) of 1 mL / min and a dropping time of 10 minutes.
  • the projection forming plating solution (D) silver plating was performed while dispersing the generated silver projection nuclei by ultrasonic stirring (projection formation step). Thereafter, the particles are taken out by filtration, washed with water, and dried, whereby a silver metal part (the thickness of the whole metal part in the part having no protrusions: 0.1 ⁇ m) is arranged on the surface of the base particle A.
  • a metal-containing particle comprising a metal part having a plurality of protrusions on the surface was obtained.
  • Example 6 The suspension (A) obtained in Example 1 was placed in a solution containing 500 ppm of potassium cyanide, 10 g / L of potassium cyanide, and 10 g / L of potassium hydroxide to obtain a particle mixture (B).
  • the electroless silver plating solution (C) was gradually added dropwise to the dispersed particle mixture (B) adjusted to 80 ° C. to form needle-like protrusions.
  • the dropping rate of the electroless silver plating solution (C) was 10 mL / min, and the dropping time was 60 minutes, and electroless silver plating was performed (acicular protrusion formation and silver plating step). Thereafter, the particles are taken out by filtration, washed with water, and dried, whereby a silver metal part (the thickness of the whole metal part in the part where there is no protrusion: 0.1 ⁇ m) is arranged on the surface of the resin particles, Metal-containing particles provided with a silver metal portion on which a plurality of needle-like protrusions were formed were obtained.
  • Example 7 The suspension (A) obtained in Example 1 was placed in a solution containing 500 ppm of potassium cyanide, 10 g / L of potassium cyanide, and 10 g / L of potassium hydroxide to obtain a particle mixture (B).
  • a silver plating solution (D) prepared by adjusting a mixed solution containing silver nitrate 30 g / L, succinimide 100 g / L, and formaldehyde 20 g / L to pH 8.0 with aqueous ammonia is prepared. did.
  • a plating solution for forming a protrusion (E) (pH 10.0) containing dimethylamine borane 100 g / L and sodium hydroxide 0.5 g / L was prepared.
  • the electroless silver plating solution (C) was gradually added dropwise to the dispersed particle mixture (B) adjusted to 80 ° C. to form needle-like protrusions.
  • the dropping rate of the electroless silver plating solution (C) was 10 mL / min, the dropping time was 45 minutes, and electroless silver plating was performed (acicular protrusion formation and silver plating step).
  • the particles were taken out by filtration, and a particle (F) having a silver metal part on the surface of the base particle A and having a metal part having a needle-like convex part on the surface was obtained.
  • the particle mixture (G) was obtained by adding and dispersing the particles (F) in 500 parts by weight of distilled water.
  • the silver plating solution (D) was gradually dropped into the dispersed particle mixture (G) adjusted to 60 ° C. to perform electroless silver plating.
  • the dropping rate of the silver plating solution (D) was 10 mL / min, the dropping time was 30 minutes, and electroless silver plating was performed.
  • the protrusion forming plating solution (E) was gradually dropped to form protrusions.
  • the protrusion formation was performed at a dropping rate of the plating solution for forming protrusions (E) of 1 mL / min and a dropping time of 10 minutes.
  • silver plating was performed while dispersing the generated silver projection nuclei by ultrasonic stirring (projection formation step).
  • the particles are taken out by filtration, washed with water, and dried, whereby a silver metal part (the thickness of the entire metal part in the part having no convex part: 0.1 ⁇ m) is arranged on the surface of the base particle A.
  • a silver metal part (the thickness of the entire metal part in the part having no convex part: 0.1 ⁇ m) is arranged on the surface of the base particle A.
  • grains provided with the metal part which has a some needle-like convex part on the surface and has a some protrusion on the surface of a convex part were obtained.
  • Example 8 The suspension (B) obtained in Example 1 was put in a solution containing 50 g / L of nickel sulfate, 30 ppm of thallium nitrate and 20 ppm of bismuth nitrate to obtain a particle mixture (C).
  • an electroless nickel-tungsten-boron alloy plating solution a mixed solution containing nickel sulfate 100 g / L, sodium tungstate 5 g / L, dimethylamine borane 30 g / L, bismuth nitrate 10 ppm, and trisodium citrate 30 g / L.
  • An electroless nickel-tungsten-boron alloy plating solution (D) adjusted to pH 6 with sodium hydroxide was prepared.
  • a silver plating solution (E) prepared by adjusting a mixed solution of silver nitrate 30 g / L, succinimide 100 g / L, and formaldehyde 20 g / L to pH 8.0 with aqueous ammonia was prepared. .
  • a plating solution for forming a protrusion (F) (pH 10.0) containing dimethylamine borane 100 g / L and sodium hydroxide 0.5 g / L was prepared.
  • the electroless nickel-tungsten-boron alloy plating solution (D) was gradually added dropwise to the dispersed particle mixture (C) adjusted to 60 ° C. to perform electroless nickel-tungsten-boron alloy plating.
  • the electroless nickel-tungsten-boron alloy plating solution (D) was dropped at a rate of 15 mL / min and the dropping time was 60 minutes to perform electroless nickel-tungsten-boron alloy plating.
  • the particles are taken out and washed with water, whereby a nickel-tungsten-boron alloy metal layer is disposed on the surface of the base material particle A, and a convex portion is formed on the surface.
  • grains provided with the metal part which has were obtained.
  • the particles were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a particle mixture (H).
  • the silver plating solution (E) was gradually added dropwise to the dispersed particle mixture (H) adjusted to 60 ° C. to perform electroless silver plating.
  • the dropping rate of the silver plating solution (E) was 10 mL / min, the dropping time was 30 minutes, and electroless silver plating was performed.
  • the protrusion forming plating solution (F) was gradually dropped to form protrusions. Protrusion formation was performed at a dropping rate of the plating solution for forming protrusions (F) of 1 mL / min and a dropping time of 10 minutes.
  • protrusion forming plating solution (F) silver plating was performed while dispersing the generated silver protrusion nuclei by ultrasonic stirring (protrusion forming step). Thereafter, the particles are removed by filtration, washed with water, and dried, whereby the nickel-tungsten-boron alloy and the silver metal part (the thickness of the entire metal part in the part having no protrusions: 0 on the surface of the base particle A: 0 0.1 ⁇ m) was obtained, and metal-containing particles were obtained that had a plurality of convex portions on the surface and a metal portion having a plurality of protrusions on the surface of the convex portions.
  • Example 9 The suspension (B) obtained in Example 1 was put in a solution containing 50 g / L of nickel sulfate, 30 ppm of thallium nitrate and 20 ppm of bismuth nitrate to obtain a particle mixture (C).
  • an electroless nickel-tungsten-boron alloy plating solution a mixed solution containing nickel sulfate 100 g / L, sodium tungstate 2 g / L, dimethylamine borane 30 g / L, bismuth nitrate 10 ppm, and trisodium citrate 30 g / L.
  • An electroless nickel-tungsten-boron alloy plating solution (D) adjusted to pH 6 with sodium hydroxide was prepared.
  • potassium gold cyanide 30 g / L potassium gold cyanide 30 g / L
  • potassium cyanide 2 g / L trisodium citrate 30 g / L
  • ethylenediaminetetraacetic acid 15 g / L potassium hydroxide 10 g / L
  • dimethylamine borane 20 g / L A gold plating solution (E) in which the mixed solution containing L was adjusted to pH 8.0 with potassium hydroxide was prepared.
  • a plating solution for forming a protrusion (F) (pH 10.0) containing 30 g / L of sodium borohydride and 0.5 g / L of sodium hydroxide was prepared.
  • the electroless nickel-tungsten-boron alloy plating solution (D) was gradually added dropwise to the dispersed particle mixture (C) adjusted to 60 ° C. to perform electroless nickel-tungsten-boron alloy plating.
  • the electroless nickel-tungsten-boron alloy plating solution (D) was dropped at a rate of 15 mL / min and the dropping time was 60 minutes to perform electroless nickel-tungsten-boron alloy plating. In this way, a particle (G) having a nickel-tungsten-boron alloy metal part disposed on the surface of the substrate particle A and having a metal part having a convex part on the surface was obtained.
  • the particles are taken out and washed with water, whereby a nickel-tungsten-boron alloy metal part is arranged on the surface of the base particle A, and a convex part is formed on the surface.
  • the particles were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a particle mixture (H).
  • the electroless gold plating solution (E) was gradually added dropwise to the dispersed particle mixture (H) adjusted to 60 ° C. to perform electroless gold plating.
  • the electroless gold plating solution (E) was dropped at a rate of 10 mL / min, and the dropping time was 30 minutes.
  • the protrusion forming plating solution (F) was gradually dropped to form protrusions. Protrusion formation was performed at a dropping rate of the plating solution for forming protrusions (F) of 1 mL / min and a dropping time of 5 minutes.
  • gold plating was performed while dispersing the generated gold protrusion nuclei by ultrasonic stirring (protrusion forming step).
  • the particles are taken out by filtration, washed with water, and dried to obtain a nickel-tungsten-boron alloy and a gold metal part on the surface of the base particle A (the thickness of the entire metal part in the part having no protrusions: 0). 0.1 ⁇ m) was obtained, and metal-containing particles were obtained that had a plurality of convex portions on the surface and a metal portion having a plurality of protrusions on the surface of the convex portions.
  • Example 10 The suspension (B) obtained in Example 1 was put in a solution containing 20 g / L of copper sulfate and 30 g / L of ethylenediaminetetraacetic acid to obtain a particle mixture (C).
  • an electroless copper plating solution a mixed solution containing 250 g / L of copper sulfate, 150 g / L of ethylenediaminetetraacetic acid, 100 g / L of sodium gluconate, and 50 g / L of formaldehyde is adjusted to pH 10.5 with ammonia.
  • a plating solution (D) was prepared.
  • tin chloride 20 g / L As electroless tin plating solutions, tin chloride 20 g / L, nitrilotriacetic acid 50 g / L, thiourea 2 g / L, thiomalic acid 1 g / L, ethylenediaminetetraacetic acid 7.5 g / L, and titanium trichloride 15 g / L
  • a tin plating solution (E) was prepared by adjusting the pH of the mixed solution containing sulfuric acid to 7.0 with sulfuric acid.
  • the copper plating solution (D) was gradually added dropwise to the dispersed particle mixture (C) adjusted to 55 ° C. to perform electroless copper plating.
  • the dropping rate of the copper plating solution (D) was 30 mL / min, the dropping time was 30 minutes, and electroless copper plating was performed. Thereafter, the particles are taken out by filtration, and in this way, a particle mixed solution (G) containing particles having a metal part in which the copper metal part is arranged on the surface of the base particle A and has a convex part on the surface. )
  • the particles are taken out and washed with water, thereby arranging a copper metal part on the surface of the substrate particle A, and a metal part having a convex part on the surface. Particles were obtained. The particles were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a particle mixture (H).
  • the tin plating solution (E) was gradually added dropwise to the dispersed particle mixture (H) adjusted to 60 ° C. to perform electroless tin plating.
  • the dropping rate of the tin plating solution (E) was 10 mL / min, the dropping time was 30 minutes, and electroless tin plating was performed.
  • the protrusion forming plating solution (F) was gradually dropped to form protrusions. Protrusion formation was performed at a dropping rate of the plating solution for forming protrusions (F) of 1 mL / min and a dropping time of 10 minutes.
  • Example 11 (1) Preparation of silicone oligomer In a 100 ml separable flask placed in a hot tub, 1 part by weight of 1,3-divinyltetramethyldisiloxane and 20 parts by weight of 0.5 wt% p-toluenesulfonic acid aqueous solution were added. I put it in. After stirring at 40 ° C. for 1 hour, 0.05 part by weight of sodium bicarbonate was added.
  • aqueous solution B was prepared by mixing 80 parts by weight of a 5 wt% aqueous solution of “GOHSENOL GH-20” manufactured by Synthetic Chemical Co., Ltd. After the said solution A was put into the separable flask installed in the warm bath, the said aqueous solution B was added.
  • the base particle A was changed to the base particle B, and a metal part was formed in the same manner as in Example 1 to obtain metal-containing particles.
  • Silicone particles (base particle C) having a particle size of 3.0 ⁇ m were obtained by using an acrylic silicone oil at both ends (“X-22-2445” manufactured by Shin-Etsu Chemical Co., Ltd.) instead of the silicone oligomer.
  • the base particle A was changed to the base particle C, and a metal part was formed in the same manner as in Example 1 to obtain metal-containing particles.
  • the base material particle A was changed to the base material particle D, and a metal part was formed in the same manner as in Example 1 to obtain metal-containing particles.
  • the base particle A was changed to the base particle E, and a metal part was formed in the same manner as in Example 1 to obtain metal-containing particles.
  • the base particle A was changed to the base particle F, and a metal part was formed in the same manner as in Example 1 to obtain metal-containing particles.
  • the base particle A was changed to the base particle G, and a metal part was formed in the same manner as in Example 1 to obtain metal-containing particles.
  • Example 17 A base particle H having a particle diameter different from that of the base particle A and having a particle diameter of 50.0 ⁇ m was prepared.
  • the base particle A was changed to the base particle H, and a metal part was formed in the same manner as in Example 1 to obtain metal-containing particles.
  • Example 18 To a 1000 mL separable flask equipped with a four-necked separable cover, stirring blade, three-way cock, condenser and temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl-N-2-methacryloyloxyethyl A monomer composition containing 1 mmol of ammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride was weighed in ion-exchanged water so that the solid content was 5% by weight, and then at 200 rpm. The mixture was stirred and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
  • the insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
  • Example 2 10 g of the metal-containing particles obtained in Example 1 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 ⁇ m mesh filter, the product was further washed with methanol and dried to obtain metal-containing particles having insulating particles attached thereto.
  • Example 19 The suspension (B) obtained in Example 1 was put in a solution containing 50 g / L of nickel sulfate, 30 ppm of thallium nitrate and 20 ppm of bismuth nitrate to obtain a particle mixture (C).
  • an electroless nickel-phosphorus alloy plating solution a mixed solution containing nickel sulfate 100 g / L, sodium hypophosphite 30 g / L, bismuth nitrate 10 ppm, and trisodium citrate 30 g / L was adjusted to pH 6 with sodium hydroxide.
  • An adjusted electroless nickel-phosphorus alloy plating solution (D) was prepared.
  • a silver plating solution (E) prepared by adjusting a mixed solution of silver nitrate 30 g / L, succinimide 100 g / L, and formaldehyde 20 g / L to pH 8.0 with aqueous ammonia was prepared. .
  • a plating solution for forming a protrusion (F) (pH 12.0) containing 130 g / L of sodium hypophosphite and 0.5 g / L of sodium hydroxide was prepared.
  • the electroless nickel-phosphorus alloy plating solution (D) was gradually dropped into the dispersed particle mixture (C) adjusted to 65 ° C. to perform electroless nickel-phosphorus alloy plating.
  • the electroless nickel-phosphorous alloy plating solution (D) was dropped at a rate of 15 mL / min and the dropping time was 60 minutes to perform electroless nickel-phosphorus alloy plating.
  • the particles are taken out and washed with water, whereby a nickel-phosphorus alloy metal layer is disposed on the surface of the base particle A, and has a convex portion on the surface. Particles with a metal part were obtained. The particles were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a particle mixture (H).
  • the silver plating solution (E) was gradually added dropwise to the dispersed particle mixture (H) adjusted to 60 ° C. to perform electroless silver plating.
  • the dropping rate of the silver plating solution (E) was 10 mL / min, the dropping time was 30 minutes, and electroless silver plating was performed.
  • the protrusion forming plating solution (F) was gradually dropped to form protrusions. Protrusion formation was performed at a dropping rate of the plating solution for forming protrusions (F) of 1 mL / min and a dropping time of 10 minutes.
  • protrusion forming plating solution F
  • silver plating was performed while dispersing the generated silver protrusion nuclei by ultrasonic stirring (protrusion forming step). Thereafter, the particles are removed by filtration, washed with water, and dried, whereby the nickel-phosphorus alloy and the silver metal part on the surface of the base particle A (total thickness of the metal part in the part having no protrusions: 0.1 ⁇ m) ) Are arranged, and a metal-containing particle having a plurality of protrusions on the surface and a metal portion having a plurality of protrusions on the surface of the protrusions is obtained.
  • Example 20 The metal-containing particles obtained in Example 1 were subjected to an antisulfurization treatment using “New Dyne Silver” manufactured by Daiwa Kasei Co., Ltd. as a silver discoloration inhibitor.
  • Example 21 The metal-containing particles obtained in Example 1 were subjected to anti-sulfurization treatment using a 2-mercaptobenzothiazole solution as a silver anti-sulfur agent.
  • Example 1 10 parts by weight of the metal-containing particles obtained in Example 1 were dispersed in 100 parts by weight of an isopropyl alcohol solution containing 0.5% by weight of 2-mercaptobenzothiazole using an ultrasonic disperser, and then the solution was filtered. As a result, metal-containing particles having an antisulfide film formed thereon were obtained.
  • Suspension (B) was put into a solution containing nickel sulfate 50 g / L, thallium nitrate 30 ppm and bismuth nitrate 20 ppm to obtain a particle mixed solution (C).
  • a nickel plating solution (D) (pH 6.5) containing 200 g / L of nickel sulfate, 85 g / L of sodium hypophosphite, 30 g / L of sodium citrate, 50 ppm of thallium nitrate, and 20 ppm of bismuth nitrate was prepared.
  • the nickel plating solution (D) was gradually added dropwise to the dispersed particle mixture (C) adjusted to 50 ° C. to perform electroless nickel plating.
  • the dropping rate of the nickel plating solution (D) was 25 mL / min, the dropping time was 60 minutes, and electroless nickel plating was performed (Ni plating step).
  • the particles are removed by filtration, washed with water, and dried, whereby a nickel-phosphorus alloy metal part is disposed on the surface of the base particle A, and a metal part having a metal part having a protrusion on the surface is provided.
  • a metal-containing particle alloy provided (the thickness of the entire metal part in the part where no protrusions were provided: 0.1 ⁇ m) was obtained.
  • Suspension (A) was put in a solution containing nickel sulfate 50 g / L, thallium nitrate 30 ppm and bismuth nitrate 20 ppm to obtain a particle mixed solution (B).
  • a plating solution for forming a protrusion (C) (pH 11.0) containing 300 g / L of sodium hypophosphite and 10 g / L of sodium hydroxide was prepared.
  • a nickel plating solution (D) (pH 6.5) containing 200 g / L of nickel sulfate, 85 g / L of sodium hypophosphite, 30 g / L of sodium citrate, 50 ppm of thallium nitrate, and 20 ppm of bismuth nitrate was prepared.
  • the protrusion forming plating solution (C) was gradually dropped into the dispersed particle mixture (B) adjusted to 50 ° C. to form protrusions.
  • Protrusion formation was performed at a dropping speed of the plating solution for protrusion formation (C) of 20 mL / min and a dropping time of 5 minutes.
  • nickel plating was performed while dispersing the generated Ni projection nuclei by ultrasonic stirring (projection formation step). In this way, a dispersed Ni protrusion nucleus and particle mixture (E) were obtained.
  • the nickel plating solution (D) was gradually added dropwise to the dispersed Ni protrusion nuclei and the particle mixture (E) to perform electroless nickel plating.
  • the dropping rate of the nickel plating solution (D) was 25 mL / min, the dropping time was 60 minutes, and electroless nickel plating was performed.
  • nickel plating was performed while dispersing the generated Ni protrusion nuclei by ultrasonic stirring (Ni plating step).
  • the particles are taken out by filtration, washed with water, and dried, whereby the metal-containing particles are provided with a metal part having a protrusion on the surface, on which the nickel-phosphorus alloy metal part is arranged on the surface of the base particle A (The thickness of the whole metal part in a part without a protrusion: 0.1 micrometer) was obtained.
  • FE-TEM field emission transmission electron microscope
  • JEM-ARM200F manufactured by JEOL Ltd.
  • the image magnification was set to 50,000 times, and 20 metal-containing particles were randomly selected, The protrusions and protrusions of each metal-containing particle were observed.
  • the heights of the protrusions and protrusions in the obtained metal-containing particles were measured, and were arithmetically averaged to obtain the average height of the protrusions and protrusions.
  • FE-TEM field emission transmission electron microscope
  • JEM-ARM200F manufactured by JEOL Ltd.
  • the image magnification was set to 50,000 times, and 20 metal-containing particles were randomly selected, The protrusions and protrusions of each metal-containing particle were observed.
  • the base diameters of the protrusions and protrusions in the obtained metal-containing particles were measured, and arithmetically averaged to obtain the average base diameter of the protrusions and protrusions.
  • FE-TEM field emission transmission electron microscope
  • JEM-ARM200F manufactured by JEOL Ltd.
  • the image magnification was set to 1 million times, and 20 metal-containing particles were randomly selected, The protrusions of each metal-containing particle were observed.
  • the apex angles of the convex portions and the protrusions were measured, and arithmetically averaged to obtain the average of the apex angles of the convex portions and the protrusions.
  • FE-TEM field emission transmission electron microscope
  • JEM-ARM200F manufactured by JEOL Ltd.
  • the image magnification was set to 50,000 times, and 20 metal-containing particles were randomly selected, The protrusions of each metal-containing particle were observed.
  • the base diameters of the protrusions and protrusions in the obtained metal-containing particles were measured, and arithmetically averaged to determine the average diameter at the center position of the heights of the protrusions and protrusions.
  • FE-TEM field emission transmission electron microscope
  • JEM-ARM200F manufactured by JEOL Ltd.
  • the image magnification was set to 50,000 times, and 20 metal-containing particles were randomly selected, The metal part in the part without the protrusion of each metal-containing particle was observed.
  • the thickness of the whole metal part in the part without the protrusion in the obtained metal-containing particles was measured, and arithmetically averaged to obtain the thickness (average thickness) (described in the above examples and comparative examples).
  • Compressive elastic modulus of metal-containing particles (10% K value) The above-mentioned compression elastic modulus (10% K value) of the obtained metal-containing particles was measured using a micro-compression tester (“Fischer Scope H-100” manufactured by Fischer) according to the method described above at 23 ° C. did. A 10% K value was determined.
  • a transparent glass substrate having a copper electrode pattern with an L / S of 30 ⁇ m / 30 ⁇ m on the upper surface was prepared. Further, a semiconductor chip having a gold electrode pattern with L / S of 30 ⁇ m / 30 ⁇ m on the lower surface was prepared.
  • the anisotropic conductive paste immediately after production was applied to a thickness of 30 ⁇ m to form an anisotropic conductive paste layer.
  • the semiconductor chip was stacked on the anisotropic conductive paste layer so that the electrodes face each other.
  • a pressure heating head is placed on the upper surface of the semiconductor chip, and a pressure of 0.5 MPa is applied to apply the anisotropic conductive paste.
  • the layer was cured at 250 ° C. to obtain a connection structure A.
  • the electrodes were connected at a low pressure of 0.5 MPa.
  • connection structure was put into “Technobit 4000” manufactured by Kulzer and cured to prepare an embedded resin for connection structure inspection.
  • the cross section of the metal-containing particles was cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass through the vicinity of the center of the connection structure in the inspection resin.
  • connection structure A by using a scanning electron microscope (FE-SEM), by observing a cross section of the obtained connection structure A, whether or not the tip of the protrusion of the metal part of the metal-containing particle is melted and solidified is determined. Judged.
  • FE-SEM scanning electron microscope
  • connection structure A obtained by the evaluation of (10) above, the bonding state of protrusion of metal part is observed by observing a cross section of connection structure A. Was judged.
  • connection part In the connection part, the tip of the protrusion of the metal part in the metal-containing particle is melted and then solidified, and is joined to the electrode and other metal-containing particles.
  • B In the connection part, the metal part in the metal-containing particle The protrusion tips solidify after melting and are not joined to the electrodes and other metal-containing particles
  • Connection resistance is 1.0 ⁇ or less ⁇ : Connection resistance exceeds 1.0 ⁇ , 2.0 ⁇ or less ⁇ : Connection resistance exceeds 2.0 ⁇ , 3.0 ⁇ or less ⁇ : Connection resistance is 3.0 ⁇ Over 5 ⁇ or less ⁇ : Connection resistance exceeds 5 ⁇
  • connection target member As a first connection target member, a power semiconductor element having Ni / Au plating on the connection surface was prepared. As a second connection target member, an aluminum nitride substrate having a connection surface plated with Cu was prepared.
  • connection silver paste On the second connection target member, the sintered silver paste was applied to a thickness of about 70 ⁇ m to form a connection silver paste layer. Then, the said 1st connection object member was laminated
  • the obtained laminated body is preheated with a hot plate at 130 ° C. for 60 seconds, and then the laminated body is heated at 300 ° C. for 3 minutes under a pressure of 10 MPa, whereby the metal atoms contained in the sintered silver paste are obtained.
  • the connection particle B is formed by sintering the contained particles to form a connection portion including the sintered product and the metal-containing particles, and joining the first and second connection target members with the sintered product. It was.
  • connection structure was put into “Technobit 4000” manufactured by Kulzer and cured to prepare an embedded resin for connection structure inspection.
  • a cross section of the metal-containing particles was cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the connection structure in the embedded resin for inspection.
  • connection structure B by using a scanning electron microscope (FE-SEM), by observing a cross section of the obtained connection structure B, whether or not the tip of the protrusion of the metal part of the metal-containing particle is solidified after being melted is determined. Judged.
  • FE-SEM scanning electron microscope
  • connection structure B obtained by the evaluation of (13) above, the connection structure B is observed in cross section, thereby bonding state of protrusion of metal part was judged.
  • connection part In the connection part, the tip of the protrusion of the metal part in the metal-containing particle is melted and then solidified, and is joined to the electrode and other metal-containing particles.
  • B In the connection part, the metal part in the metal-containing particle The protrusion tips solidify after melting and are not joined to the electrodes and other metal-containing particles
  • connection reliability in connection structure B The connection structure B obtained by the evaluation in (13) above was put into a thermal shock tester (manufactured by Espec: TSA-101S-W), and the minimum temperature ⁇ 40 The bonding strength was measured with a shear strength tester (manufactured by Reska Co., Ltd .: STR-1000) after 3000 cycles with the treatment conditions of 1 minute at a holding temperature of 30 minutes and a maximum temperature of 200 ° C. for 30 minutes. Connection reliability was determined according to the following criteria.
  • Bonding strength is 50 MPa or more XX: Bonding strength exceeds 40 MPa, 50 MPa or less ⁇ : Bonding strength exceeds 30 MPa, 40 MPa or less ⁇ : Bonding strength exceeds 20 MPa, 30 MPa or less X: Bonding strength is 20 MPa or less
  • the above silicone copolymer was polymerized by the following method. 162 g (628 mmol) of 4,4′-dicyclohexylmethane diisocyanate (Degussa), amino terminal-modified polydimethylsiloxane (“TSF4709” manufactured by Momentive) (molecular weight 10,000) 900 g (90 mmol) The solution was dissolved at 70 to 90 ° C. and stirred for 2 hours. Thereafter, 65 g (625 mmol) of neopentyl glycol (Mitsubishi Gas Chemical Co., Ltd.) was slowly added and kneaded for 30 minutes, and then unreacted neopentyl glycol was removed under reduced pressure.
  • TEZ4709 amino terminal-modified polydimethylsiloxane
  • the obtained silicone copolymer was dissolved in isopropyl alcohol and used at 20% by weight. The disappearance of the isocyanate group was confirmed by IR spectrum.
  • the silicone content was 80% by weight
  • the weight average molecular weight was 25000
  • the SP value was 7.8
  • the SP value of the repeating unit of the structure having a polar group (polyurethane) was 10. there were.
  • silicone rubber was prepared as a base material for the continuity test member (a sheet-like base material formed of an insulating material).
  • the silicone rubber has a width of 25 mm, a width of 25 mm and a thickness of 1 mm.
  • Silicone rubber is formed with a total of 400 cylindrical through-holes having a diameter of 0.5 mm formed by laser processing with 20 vertical and 20 horizontal holes.
  • the conductive material was coated on a silicone rubber having a through hole using a knife coater, and the through hole was filled with the conductive material.
  • the silicone rubber filled with the conductive material in the through hole was dried in an oven at 50 ° C. for 10 minutes, it was further dried at 100 ° C. for 20 minutes to obtain a continuity inspection member having a thickness of 1 mm.
  • the contact resistance value of the obtained continuity test member was measured using a contact resistance measurement system ("MS7500” manufactured by Fact Kei Co.).
  • MS7500 manufactured by Fact Kei Co.
  • the conductive portion of the continuity test member obtained with a load of 15 gf was pressed from the vertical direction with a platinum probe having a diameter of 0.5 mm.
  • 5V was applied with a low resistance meter (“MODEL3566” manufactured by Tsuruga Electric Co., Ltd.), and the contact resistance value was measured.
  • An average value of contact connection resistance values obtained by measuring five conductive portions was calculated.
  • the contact resistance value was determined according to the following criteria.
  • the repeated reliability test and the contact resistance value of the obtained continuity test member were measured using a contact resistance measurement system ("MS7500” manufactured by Fact Kei Co., Ltd.).
  • MS7500 manufactured by Fact Kei Co., Ltd.
  • the conductive portion of the probe sheet obtained with a load of 15 gf with a platinum probe having a diameter of 0.5 mm was repeatedly pressed 1000 times from the vertical direction. After repeatedly pressing 1000 times, 5 V was applied with a low resistance meter (“MODEL3566” manufactured by Tsuruga Electric Co., Ltd.), and the contact resistance value was measured. An average value of contact resistance values obtained by similarly measuring five conductive portions was calculated.
  • the contact resistance value was determined according to the following criteria.
  • the spherical shape in the convex portion and the protrusion includes a partial shape of the sphere. In Comparative Examples 1 and 2, it was confirmed that the tip of the protrusion did not melt even when heated to 400 ° C.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention concerne une particule contenant du métal qui peut être liée à une autre particule ou à un autre élément par fusion de la pointe de chacune des saillies d'une partie métallique de la particule contenant du métal à une température relativement basse et par solidification d'un produit fondu après la procédure de fusion, et qui a une fiabilité de connexion améliorée. La particule contenant du métal selon la présente invention comprend une particule de base et une partie métallique qui est disposée sur la surface de la particule de base, la partie métallique ayant de multiples saillies sur sa surface externe et la pointe de chacune des saillies de la partie métallique pouvant être fondue à une température inférieure ou égale à 400 °C.
PCT/JP2017/010251 2016-03-15 2017-03-14 Particule contenant du métal, matériau de connexion, structure connectée et procédé de production de structure connectée WO2017159694A1 (fr)

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KR1020217040390A KR20210154865A (ko) 2016-03-15 2017-03-14 금속 함유 입자, 접속 재료, 접속 구조체 및 접속 구조체의 제조 방법
CN201780003651.8A CN108140450B (zh) 2016-03-15 2017-03-14 含金属的粒子、连接材料、连接结构体及连接结构体的制造方法
JP2017516171A JP7131908B2 (ja) 2016-03-15 2017-03-14 金属含有粒子、接続材料、接続構造体及び接続構造体の製造方法
KR1020187010189A KR20180120667A (ko) 2016-03-15 2017-03-14 금속 함유 입자, 접속 재료, 접속 구조체 및 접속 구조체의 제조 방법

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WO2020100992A1 (fr) * 2018-11-15 2020-05-22 積水化学工業株式会社 Particules enrobées de métal, corps connecté par particules, procédé de production d'un corps connecté par particules, matériau de connexion et structure de connexion
WO2020100991A1 (fr) * 2018-11-15 2020-05-22 積水化学工業株式会社 Corps relié par particules, matériau de connexion, structure de connexion, élément d'inspection de continuité et dispositif d'inspection de continuité
JP2022096613A (ja) * 2020-12-17 2022-06-29 株式会社ドクサンハイメタル 高強度ビーズ、及びこれを用いた導電粒子
JP7495884B2 (ja) 2018-11-15 2024-06-05 積水化学工業株式会社 金属被覆粒子、粒子連結体、粒子連結体の製造方法、接続材料及び接続構造体

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WO2020100992A1 (fr) * 2018-11-15 2020-05-22 積水化学工業株式会社 Particules enrobées de métal, corps connecté par particules, procédé de production d'un corps connecté par particules, matériau de connexion et structure de connexion
WO2020100991A1 (fr) * 2018-11-15 2020-05-22 積水化学工業株式会社 Corps relié par particules, matériau de connexion, structure de connexion, élément d'inspection de continuité et dispositif d'inspection de continuité
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JP7495884B2 (ja) 2018-11-15 2024-06-05 積水化学工業株式会社 金属被覆粒子、粒子連結体、粒子連結体の製造方法、接続材料及び接続構造体
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