WO2018235909A1 - 導電性粒子、導電性粒子の製造方法、導電材料及び接続構造体 - Google Patents

導電性粒子、導電性粒子の製造方法、導電材料及び接続構造体 Download PDF

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Publication number
WO2018235909A1
WO2018235909A1 PCT/JP2018/023660 JP2018023660W WO2018235909A1 WO 2018235909 A1 WO2018235909 A1 WO 2018235909A1 JP 2018023660 W JP2018023660 W JP 2018023660W WO 2018235909 A1 WO2018235909 A1 WO 2018235909A1
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Prior art keywords
conductive
conductive portion
particle
particles
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PCT/JP2018/023660
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English (en)
French (fr)
Japanese (ja)
Inventor
嘉代 大秦
茂雄 真原
Original Assignee
積水化学工業株式会社
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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 JP2018535199A priority Critical patent/JP7132122B2/ja
Priority to KR1020227002664A priority patent/KR20220016999A/ko
Priority to CN201880030129.3A priority patent/CN110603612B/zh
Priority to CN202210997623.5A priority patent/CN115458206A/zh
Priority to KR1020197017103A priority patent/KR102356887B1/ko
Publication of WO2018235909A1 publication Critical patent/WO2018235909A1/ja
Priority to JP2021159162A priority patent/JP7288487B2/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • 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
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • 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
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Definitions

  • the present invention relates to, for example, conductive particles that can be used for electrical connection between electrodes.
  • the present invention also relates to a method for producing the conductive particles, a conductive material using the conductive particles, and a connection structure.
  • Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
  • anisotropic conductive material conductive particles are dispersed in a binder resin.
  • conductive particles in which the surface of the conductive layer is subjected to insulation treatment may be used as the conductive particles.
  • the anisotropic conductive material is used to obtain various connection structures.
  • connection by the anisotropic conductive material for example, connection of a flexible printed substrate and a glass substrate (FOG (Film on Glass)), connection of a semiconductor chip and a flexible printed substrate (COF (Chip on Film)), semiconductor The connection between a chip and a glass substrate (COG (Chip on Glass)), the connection between a flexible printed substrate and a glass epoxy substrate (FOB (Film on Board)), and the like can be mentioned.
  • the electroconductive particle As an example of the said electroconductive particle, the electroconductive particle provided with the base material particle and the electroconductive metal layer which coat
  • the base particle is a polymer particle having a glass transition temperature (Tg) of 50 ° C. or more and 100 ° C. or less.
  • the thickness of the conductive metal layer is 0.01 ⁇ m to 0.15 ⁇ m.
  • curved panels In recent years, development of various electronic devices is in progress, and materials of substrates are also diversified. For example, curved panels, flexible panels that can be freely bent, and the like have been developed. Since flexibility is required for the above-mentioned curved panel etc., a plastic substrate such as a polyimide substrate is considered as a flexible member used for the curved panel etc. instead of the conventional glass substrate.
  • the temperature or pressure at the time of mounting needs to be as low as possible because the plastic substrate is easily deformed or broken depending on the temperature or pressure at the time of mounting. If the temperature or pressure at the time of mounting is lowered, the conductive particles can not be sufficiently deformed at the conductive connection between the electrodes. As a result, it may be difficult to secure a sufficient contact area between the conductive particles and the electrode. In addition, the action of returning the compressed conductive particles to their original shape may act to cause a phenomenon called springback. When spring back occurs, it may be difficult to maintain a sufficient contact area between the conductive particles and the electrode. As a result, the conduction reliability between the electrodes may be reduced.
  • An object of the present invention is to provide a conductive particle which can effectively enhance the reliability of conduction between electrodes and can effectively prevent the breakage of the conductive portion due to an external impact. Moreover, this invention is providing the manufacturing method of the said electroconductive particle, the electrically-conductive material using the said electroconductive particle, and a connection structure.
  • a substrate particle, a first conductive portion disposed on the surface of the substrate particle, and a second conductivity disposed on the outer surface of the first conductive portion And, when the outer surface of the second conductive portion is observed with an electron microscope, there are no pinholes whose dimension in the maximum longitudinal direction is 50 nm or more, or the dimension in the maximum longitudinal direction is Conductive particles are provided in which pinholes of 50 nm or more are present at 1 / ⁇ m 2 or less.
  • a conductive particle wherein pinholes of 50 nm or more and 200 nm or less are present at 1 piece / ⁇ m 2 or less.
  • the conductive particle satisfies the relationship of the following formula (1), and the compression recovery rate at 25 ° C. is 10% or less.
  • A is 10% K value (N / mm ⁇ 2 >) of the said electroconductive particle
  • B is an average particle diameter (micrometer) of the said electroconductive particle.
  • the average particle size is 3 ⁇ m or more and 30 ⁇ m or less.
  • the second conductive portion contains gold, silver, palladium, platinum, copper, cobalt, ruthenium, indium or tin.
  • the ionization tendency of the metal contained in the first conductive portion is larger than the ionization tendency of the metal contained in the second conductive portion.
  • the first conductive portion includes nickel and phosphorus.
  • the content of phosphorus on the second conductive portion side in the first conductive portion is the first content. It is larger than the content of phosphorus on the side of the base particle in the conductive part.
  • an electroconductive particle comprising a substrate particle and a first electroconductive portion disposed on the surface of the substrate particle is used on the outer surface of the first electroconductive portion.
  • a method of producing a conductive particle wherein the second conductive portion is formed such that there is no pinhole or a pinhole with a dimension in the maximum length direction of 50 nm or more is 1 piece / ⁇ m 2 or less.
  • a conductive material comprising the above-described conductive particles and a binder resin.
  • a first connection target member having a first electrode on the surface
  • a second connection target member having a second electrode on the surface
  • the first connection target member And a connecting portion connecting the second connection target member, wherein the material of the connecting portion is the above-described conductive particle, or a conductive material including the conductive particle and a binder resin
  • a connection structure is provided in which the first electrode and the second electrode are electrically connected by the conductive particles.
  • the conductive particle according to the present invention comprises a base particle, a first conductive portion disposed on the surface of the base particle, and a second conductive portion disposed on the outer surface of the first conductive portion. And a unit.
  • the conductive particle according to the present invention when the outer surface of the second conductive portion is observed with an electron microscope, there is no pinhole having a dimension of 50 nm or more in the maximum length direction, or the maximum length There are pinholes with a dimension of 50 nm or more at 1 piece / ⁇ m 2 or less.
  • the conductive particle according to the present invention has the above-described configuration, so that the conduction reliability between the electrodes can be effectively improved, and cracking of the conductive portion due to an external impact can be effectively prevented.
  • the conductive particle according to the present invention comprises a base particle, a first conductive portion disposed on the surface of the base particle, and a second conductive portion disposed on the outer surface of the first conductive portion. And a unit.
  • the conductive particle according to the present invention when the outer surface of the second conductive portion is observed with an electron microscope, there is no pinhole having a dimension of 50 nm or more in the maximum length direction, or the maximum length There are pinholes with a dimension of 50 nm or more and 200 nm or less at 1 piece / ⁇ m 2 or less.
  • the conductive particle according to the present invention has the above-described configuration, so that the conduction reliability between the electrodes can be effectively improved, and cracking of the conductive portion due to an external impact can be effectively prevented.
  • a method of producing conductive particles according to the present invention comprises using a conductive particle comprising a base material particle and a first conductive portion disposed on the surface of the base material particle.
  • a step of disposing a second conductive portion by plating on the outer surface is provided.
  • the method of producing a conductive particle according to the present invention when the outer surface of the second conductive portion is observed with an electron microscope, there is no pinhole having a dimension of 50 nm or more in the maximum length direction, or The second conductive portion is formed such that a pinhole having a dimension of 50 nm or more in the maximum length direction is present at 1 piece / ⁇ m 2 or less.
  • the method for producing conductive particles according to the present invention has the above-described configuration, so that the reliability of conduction between electrodes can be effectively improved, and cracking of the conductive portion due to external impact can be effectively prevented. Can.
  • FIG. 1 is a cross-sectional view showing a conductive particle according to a first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing a conductive particle according to a second embodiment of the present invention.
  • FIG. 3 is sectional drawing which shows typically the bonded structure using the electroconductive particle which concerns on the 1st Embodiment of this invention.
  • FIG. 4 is a view showing an image of the surface of the conductive particle produced in Example 1.
  • FIG. 5 is a view showing an image of the surface of the conductive particle produced in Comparative Example 1.
  • the conductive particle according to the present invention comprises a substrate particle, a first conductive portion disposed on the surface of the substrate particle, and a second conductive portion disposed on the surface of the first conductive portion. And
  • a pinhole having a dimension of 50 nm or more is present at 1 piece / ⁇ m 2 or less. In this case, in the conductive particle according to the present invention, when the pinholes are present, the number of the pinholes counted per 1 ⁇ m 2 is one or less.
  • the dimension in the maximum length direction of the pinholes to be counted is 50 nm or more.
  • the conductive particle according to the present invention when the outer surface of the second conductive portion is observed with an electron microscope, there is no pinhole having a dimension of 50 nm or more in the maximum length direction, or the maximum length It is preferable that a pinhole with a dimension of 50 nm or more and 200 nm or less be present at 1 piece / ⁇ m 2 or less. In this case, in the conductive particle according to the present invention, the number of pinholes counted per 1 ⁇ m 2 is one or less. In the conductive particle according to the present invention, the dimension of the pinhole in the maximum length direction is 50 nm or more and 200 nm or less.
  • the conduction reliability between the electrodes can be effectively improved, and the cracking of the conductive portion due to an external impact can be effectively prevented.
  • conductive particles having relatively flexible substrate particles are easily cracked in the conductive portion by external impact.
  • the inventors of the present invention conducted intensive studies to suppress cracking of the conductive portion due to an external impact, and as a result, the cracking of the conductive portion due to the external impact is a pinhole generated by the replacement gold plating process forming the conductive portion of the conductive particle. Was found to be the cause.
  • the present inventors have found that, in conductive particles having relatively flexible base particles, cracking of the conductive portion occurs due to external impact starting from pinholes. In the present invention, since the above configuration is provided, it is possible to effectively prevent the conductive part from being broken due to an external impact.
  • the pinhole is formed, for example, by elution of nickel as ions on the surface of the first conductive portion formed by nickel plating when forming the second conductive portion by replacement gold plating. .
  • the missing portion of the first conductive portion is a pinhole.
  • the conductive particle according to the present invention when the outer surface of the second conductive portion is observed with an electron microscope, it is preferable that no pinhole having a dimension of 50 nm or more in the maximum length direction exists.
  • the pinhole having a dimension of 50 nm or more in the maximum longitudinal direction is It exists in 1 piece / ⁇ m 2 or less.
  • the number of pinholes having a dimension of 50 nm or more in the maximum length direction be 0.1 / ⁇ m 2 or less.
  • the conductive particle according to the present invention when the outer surface of the second conductive portion is observed with an electron microscope, it is preferable that no pinhole whose dimension in the maximum length direction is 50 nm or more and 200 nm or less is present.
  • a pin having a dimension of 50 nm or more and 200 nm or less in the maximum length direction when the pinhole is present there are 1 hole / ⁇ m 2 or less.
  • the above-mentioned pinhole of which the dimension in the maximum length direction is 50 nm or more The dimension in the maximum longitudinal direction is preferably 150 nm or less, more preferably 100 nm or less.
  • the number of pinholes having a dimension of 50 nm or more and 200 nm or less in the maximum length direction be 0.1 pieces / ⁇ m 2 or less .
  • the conduction reliability between the electrodes can be more effectively enhanced, and the cracking of the conductive portion due to external impact can be more effectively prevented. it can.
  • the presence or absence of the pinhole can be confirmed, for example, by observing any conductive particle with an electron microscope. Specifically, the presence or absence of the above-mentioned pinhole is confirmed by observing an arbitrary five places with an electron microscope about a portion which excluded a 0.5 micrometer part from the perimeter of arbitrary conductive particles inward. be able to.
  • the dimension in the maximum longitudinal direction of the pinhole can be calculated, for example, by observing any conductive particle with an electron microscope.
  • the dimension in the maximum length direction of the pinhole is a distance obtained by connecting two points on the outer periphery of the pinhole by a straight line, and the dimension obtained by connecting the two points on the outer periphery of the pinhole by a straight line is the largest.
  • the shape of the pinhole is not particularly limited.
  • the shape of the pinhole may be circular or may be other than circular.
  • the dimension in the maximum length direction of the pinhole corresponds to the maximum diameter.
  • a minute region in which the conductive portion is not formed may be formed.
  • the maximum longitudinal dimension of such a region is generally less than 50 nm, and in the present invention such small regions are not included in the pinholes.
  • the conductive particles preferably satisfy the relationship of the following formula (1).
  • A is 10% K value (N / mm ⁇ 2 >) of the said electroconductive particle
  • B is an average particle diameter (micrometer) of the said electroconductive particle.
  • 10% K value of the conductive particles is preferably 500 N / mm 2 or more, more preferably 1000 N / mm 2 or more, preferably 4500N / Mm ⁇ 2 > or less, More preferably, it is 4000 N / mm ⁇ 2 > or less.
  • the 10% K value (the compression modulus when the conductive particles are compressed by 10%) of the conductive particles can be measured as follows.
  • the 10% K value (10% compression modulus) at 25 ° C. can be determined by the following equation.
  • the micro compression tester for example, “Micro compression tester MCT-W200” manufactured by Shimadzu Corporation, “Fisher Scope H-100” manufactured by Fisher, etc. may be used.
  • the 10% K value at 25 ° C. of the conductive particles is preferably calculated by averaging the 10% K values at 25 ° C. of 50 arbitrarily selected conductive particles.
  • the above-mentioned K value expresses the hardness of conductive particles universally and quantitatively.
  • the hardness of the conductive particles can be quantitatively and uniquely represented.
  • the compression recovery rate at 25 ° C. of the conductive particles is preferably 10% or less, more preferably 8% or less.
  • the lower limit of the compression recovery rate at 25 ° C. of the conductive particles is not particularly limited.
  • the compression recovery rate at 25 ° C. of the conductive particles may be 3% or more.
  • the compression recovery rate at 25 ° C. of the conductive particles can be measured as follows.
  • the load reverse load value
  • the origin load value (0.40 mN)
  • the load-compression displacement can be measured during this time, and the compression recovery rate at 25 ° C. can be determined from the following equation.
  • the loading speed is 0.33 mN / sec.
  • the micro compression tester for example, “Micro compression tester MCT-W200” manufactured by Shimadzu Corporation, “Fisher Scope H-100” manufactured by Fisher, etc. may be used.
  • Compression recovery rate (%) [L2 / L1] ⁇ 100
  • L1 Compressive displacement from the home load value to the reverse load value when applying a load
  • L2 Unloaded displacement from the reverse load value to the home load value when releasing the load
  • the electroconductive particle can be used suitably for the conductive connection application in a curved part.
  • the conductive particles are used for conductive connection in a curved portion, particularly excellent conduction reliability is effectively exhibited.
  • the conductive particles have the above-described compression characteristics, and thus can be suitably used for conductive connection of electrodes of a flexible member, and preferably used for conductive connection of electrodes of a flexible member in a curved state. it can. By using the conductive particles, the flexible member can be used in a curved state while exhibiting high conduction reliability.
  • connection structure using a flexible member a flexible panel etc. are mentioned.
  • Flexible panels can be used as curved panels.
  • the conductive particles are preferably used to form a connection of a flexible panel, and are preferably used to form a connection of a curved panel.
  • the average particle diameter of the conductive particles is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, still more preferably 7 ⁇ m or more, particularly preferably 10 ⁇ m or more, preferably 1000 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 30 ⁇ m. Or less, particularly preferably 25 ⁇ m or less, and most preferably 20 ⁇ m or less.
  • Conductive particles can be suitably used for conductive connection applications as the average particle diameter of the above-mentioned conductive particles is 3 micrometers or more and 30 micrometers or less. When the average particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively lowered, and the conduction reliability between the electrodes can be further effectively enhanced. be able to.
  • the average particle size of the conductive particles is more preferably a number average particle size.
  • the average particle diameter of the conductive particles is, for example, 50 arbitrary conductive particles observed with an electron microscope or an optical microscope to calculate an average value, or a plurality of measurements using a laser diffraction type particle size distribution measuring device It is obtained by calculating the average value of the results.
  • the coefficient of variation of the particle diameter of the conductive particles is preferably as low as possible, but is usually 0.1% or more, preferably 10% or less, more preferably 8% or less, and still more preferably 5% or less.
  • the conduction reliability can be further enhanced when the coefficient of variation of the particle diameter of the conductive particles is at least the lower limit and at the upper limit.
  • the variation coefficient of the particle diameter of the conductive particles may be less than 5%.
  • the coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle diameter of conductive particles Dn: Average value of particle diameters of conductive particles
  • the shape of the conductive particles is not particularly limited.
  • the shape of the conductive particles may be spherical or may be a shape other than a spherical shape such as a flat shape.
  • FIG. 1 is a cross-sectional view showing a conductive particle according to a first embodiment of the present invention.
  • the conductive particle 1 shown in FIG. 1 includes base particles 2, a first conductive portion 3, and a second conductive portion 4.
  • the first conductive portion 3 is disposed on the surface of the base particle 2.
  • the second conductive portion 4 is disposed on the surface of the first conductive portion 3.
  • the first conductive portion 3 is disposed between the base particle 2 and the second conductive portion 4.
  • the first conductive portion 3 is in contact with the surface of the base particle 2.
  • the first conductive portion 3 covers the surface of the base particle 2.
  • the second conductive portion 4 is in contact with the surface of the first conductive portion 3.
  • the second conductive portion 4 covers the surface of the first conductive portion 3.
  • the conductive particle 1 is a coated particle in which the surface of the base particle 2 is covered with the first conductive portion 3 and the second conductive portion 4.
  • the second conductive portion 4 is located on the outermost surface of the conductive portion and is the outermost layer.
  • a multilayer conductive portion is formed.
  • the presence state of the pinhole satisfies the above-described configuration.
  • the first conductive portion 3 covers the entire surface of the base particle 2 and forms a conductive layer.
  • the first conductive portion may cover the entire surface of the base particle, or may not cover the entire surface of the base particle.
  • the first conductive portion may form a conductive layer covering the entire surface of the base particle, or may not form a conductive layer covering the entire surface of the base particle.
  • the first conductive portion may be a conductive layer.
  • the conductive particles may have a region in which the base particles are not covered by the first conductive portion.
  • the second conductive portion 4 covers the entire surface of the first conductive portion 3 and forms a conductive layer.
  • the second conductive portion may cover the entire surface of the first conductive portion, or may not cover the entire surface of the first conductive portion.
  • the second conductive portion may form a conductive layer covering the entire surface of the first conductive portion, and may not form a conductive layer covering the entire surface of the first conductive portion .
  • the second conductive portion may be a conductive layer.
  • the conductive particle may have a region in which the first conductive portion is not covered by the second conductive portion.
  • the conductive particles 1 do not have a core substance.
  • the conductive particle 1 has no protrusion on the outer surface of the conductive part.
  • the conductive particles 1 are spherical.
  • the first conductive portion 3 and the second conductive portion 4 have no protrusion on the outer surface.
  • the conductive particle according to the present invention may have no protrusion on the surface of the conductive portion, and may have a spherical shape.
  • the conductive particles 1 do not have an insulating substance.
  • the conductive particles 1 may have an insulating material disposed on the outer surface of the second conductive portion 4.
  • the first conductive portion 3 is directly laminated on the surface of the base particle 2.
  • another conductive portion may be disposed between the base particle and the first conductive portion.
  • the first conductive portion may be disposed on the surface of the base particle via another conductive portion.
  • FIG. 2 is a cross-sectional view showing a conductive particle according to a second embodiment of the present invention.
  • the conductive particle 21 shown in FIG. 2 includes a base particle 2, a first conductive portion 22, a second conductive portion 23, a plurality of core materials 24, and an insulating material 25.
  • the first conductive portion 22 is disposed on the surface of the base particle 2.
  • the second conductive portion 23 is disposed on the surface of the first conductive portion 22.
  • the plurality of core substances 24 are disposed on the surface of the base particle 2.
  • the first conductive portion 22 and the second conductive portion 23 cover the base particle 2 and the plurality of core substances 24.
  • the conductive particles 21 are coated particles in which the surfaces of the base particle 2 and the core material 24 are coated with the first conductive portion 22 and the second conductive portion 23.
  • the conductive particle 21 has a plurality of protrusions 21 a on the outer surface of the conductive portion.
  • the first conductive portion 22 and the second conductive portion 23 have a plurality of protrusions 22 a and 23 a on the outer surface.
  • the plurality of core materials 24 are embedded in the first conductive portion 22 and the second conductive portion 23.
  • the core material 24 is disposed inside the protrusions 21a, 22a and 23a.
  • the outer surfaces of the first conductive portion 22 and the second conductive portion 23 are raised by the plurality of core substances 24, and the protrusions 21a, 22a and 23a are formed.
  • the conductive particles may have projections on the outer surface of the conductive portion.
  • the conductive particle may have no protrusion on the outer surface of the first conductive portion and may have a protrusion on the outer surface of the second conductive portion.
  • the conductive particles may include a plurality of core materials that raise the surface of the second conductive portion so as to form a plurality of protrusions inside or inside the second conductive portion.
  • the core material may be located inside the first conductive portion, may be located inside the first conductive portion, or may be located outside the first conductive portion.
  • a plurality of core materials 24 are used to form the protrusions 21a, 22a and 23a.
  • a plurality of the core substances may not be used to form the protrusions.
  • the conductive particles may not have a plurality of the core substances.
  • the conductive particles 21 have an insulating material 25 disposed on the outer surface of the second conductive portion 23. At least a partial region of the outer surface of the second conductive portion 23 is covered with the insulating material 25.
  • the insulating material 25 is formed of an insulating material and is an insulating particle.
  • the conductive particles may have an insulating material disposed on the outer surface of the conductive portion. However, the conductive particles may not necessarily have an insulating substance.
  • (meth) acrylic means one or both of “acrylic” and “methacrylic”
  • (meth) acrylate means one or both of “acrylate” and “methacrylate”.
  • the substrate particles include resin particles, inorganic particles other than metal particles, organic-inorganic hybrid particles, metal particles and the like.
  • 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 particle may be a core-shell particle comprising a core and a shell disposed on the surface of the core.
  • the base material particles are more preferably resin particles or organic-inorganic hybrid particles, and may be resin particles or organic-inorganic hybrid particles.
  • the said electroconductive particle When connecting between electrodes using the said electroconductive particle, after arrange
  • the substrate particles are resin particles or organic-inorganic hybrid particles, the conductive particles are easily deformed during the pressure bonding, and the contact area between the conductive particles and the electrode becomes large. Therefore, the conduction reliability between the electrodes is further enhanced.
  • the material of 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; polyalkylene terephthalates and polycarbonates , Polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene oxide, polyacetal, Polyimide, polyamide imide, polyether ether ketone, polyester Terusuruhon, and polymers such as obtained by a variety of polymerizable monomer having an terephthalates and polycarbonates , Polyamide, phenol formalde
  • the material of the resin particles is ethylenic. It is preferable that it is a polymer obtained by polymerizing one or more kinds of polymerizable monomers having an unsaturated group.
  • the resin particle is obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group
  • a non-crosslinkable monomer may be used as the polymerizable monomer having an ethylenically unsaturated group.
  • crosslinkable monomers may be used as the polymerizable monomer having an ethylenically unsaturated group.
  • non-crosslinkable monomers examples include styrene-based monomers such as styrene and ⁇ -methylstyrene; carboxyl-containing monomers such as (meth) acrylic acid, maleic acid and maleic anhydride; Meta) 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 meta) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate and the like Oxygen
  • crosslinkable monomer examples include, for example, tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipentamer.
  • the said resin particle can be obtained by polymerizing the polymerizable monomer which has the said ethylenically unsaturated group by a well-known method.
  • this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of swelling and polymerizing a monomer with a radical polymerization initiator using non-crosslinked seed particles.
  • the substrate particles are inorganic particles or organic-inorganic hybrid particles other than metal particles
  • examples of the inorganic substance that is the material of the substrate particles include silica, alumina, barium titanate, zirconia, carbon black and the like. It is preferable that the said inorganic substance is not a metal.
  • the particles formed of the above 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, baking is carried out as necessary. The particles obtained by carrying out are mentioned.
  • examples the organic-inorganic hybrid particle
  • the organic-inorganic hybrid particle is preferably a core-shell type organic-inorganic hybrid particle having a core and a shell disposed on the surface of the core. It is preferable that the said core is an organic core. It is preferable that the said shell is an inorganic shell. From the viewpoint of further effectively reducing the connection resistance between the electrodes, the base material particle is preferably an organic-inorganic hybrid particle having an organic core and an inorganic shell disposed on the surface of the organic core. .
  • the material of the resin particle mentioned above, etc. are mentioned.
  • the inorganic substance mentioned as a material of the base material particle mentioned above is mentioned.
  • the material of 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 by a sol-gel method and then firing the shell.
  • the metal alkoxide is preferably a silane alkoxide.
  • the inorganic shell is preferably formed of a silane alkoxide.
  • the base particle is a metal particle
  • examples of the metal that is the material of the metal particle include silver, copper, nickel, silicon, gold and titanium.
  • the said base material particle is not a metal particle.
  • the particle diameter of the substrate particle is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, still more preferably 2.5 ⁇ m or more, particularly preferably 3 ⁇ m or more, preferably 1000 ⁇ m or less, more preferably 100 ⁇ m or less, more preferably Is 30 ⁇ m or less, particularly preferably 5 ⁇ m or less.
  • the particle diameter of the above-mentioned base material particle is above the above-mentioned lower limit or above the above-mentioned lower limit, the contact area between the conductive particle and the electrode becomes large, and the conduction reliability between the electrodes is further enhanced.
  • the connection resistance between the connected electrodes can be further effectively lowered.
  • the conductive particles are easily compressed sufficiently, and the connection resistance between the electrodes connected via the conductive particles is further effectively reduced. it can.
  • the distance between the electrodes is reduced and the thickness of the conductive portion is increased, small conductive particles can be obtained.
  • the particle diameter of the substrate particle indicates a diameter when the substrate particle is spherical, and indicates a maximum diameter when the substrate particle is not spherical.
  • the particle diameter of the base particle indicates a number average particle diameter.
  • the particle diameter of the substrate particles can be determined using a particle size distribution measuring device or the like.
  • the particle diameter of the substrate particles is preferably determined by observing 50 arbitrary substrate particles with an electron microscope or an optical microscope and calculating an average value. In the case of measuring the particle diameter of the above-mentioned base material particle in the conductive particle, it can be measured, for example, as follows.
  • the conductive particle has a first conductive portion.
  • the metal which is the material of the first conductive portion is not particularly limited. Examples of the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon and the like. Alloys and the like. Moreover, tin-doped indium oxide (ITO), a solder, etc. are mentioned as said metal. As the metal that is the material of the first conductive portion, only one type may be used, or two or more types may be used in combination.
  • the metal that is the material of the first conductive portion is preferably an alloy containing tin, nickel, palladium, copper or gold, and nickel or nickel More preferably, it is palladium.
  • the first conductive portion preferably contains nickel and phosphorus.
  • the first conductive portion is preferably a conductive portion containing nickel, and preferably contains nickel as a main metal.
  • the content of nickel in 100% by weight of the first conductive portion is preferably 10% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, still more preferably 70% by weight or more Preferably it is 90 weight% or more.
  • the content of nickel in 100% by weight of the first conductive portion may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more. When the content of nickel in the first conductive portion is equal to or more than the above lower limit, the conduction reliability between the electrodes can be more effectively enhanced.
  • the content of phosphorus in 100% by weight of the first conductive portion is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 15% by weight or less, more preferably 10% by weight % Or less.
  • connection resistance between the electrodes is further effectively reduced.
  • the first conductive portion in the thickness direction of the first conductive portion The content of phosphorus on the side of the second conductive portion in the conductive portion is preferably larger than the content of phosphorus on the side of the base particle on the first conductive portion.
  • the content of phosphorus in an area of 100% by weight from the second conductive part side of the first conductive part toward the inside in a thickness 1/2 area is the first conductive It is preferable that the content is greater than the phosphorus content in 100% by weight of the area from the base material particle side of the part to the outside from the thickness 1/2 area (the area of 50% thickness on the inner surface side).
  • the inter-electrode conduction reliability is achieved because the content of phosphorus in the 100% by weight area of 50% thickness on the outer surface side is larger than the content of phosphorus in the 100% by weight area of 50% thickness on the inner surface side It is possible to more effectively improve the resistance and to prevent the breakage of the conductive portion due to the external impact more effectively.
  • the content of phosphorus in an area of 100% by weight from the second conductive part side of the first conductive part toward the inside in a half thickness area (50% thickness area on the outer surface side) is preferably 1 weight % Or more, more preferably 3% by weight or more, preferably 15% by weight or less, more preferably 10% by weight or less.
  • the content of phosphorus in the 100% by weight area having a thickness of 50% on the outer surface side is greater than or equal to the lower limit and less than the upper limit, the conduction reliability between the electrodes can be more effectively enhanced. It is possible to more effectively prevent cracking of the conductive portion due to impact.
  • the content of phosphorus in 100% by weight of a region (a region with a thickness of 50% on the inner surface side) from the base particle side of the first conductive portion to the outside toward the outside is preferably 0.1 weight % Or more, more preferably 0.5% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less.
  • the content of phosphorus in the 100% by weight area having a thickness of 50% on the inner surface side is equal to or more than the above lower limit and the above upper limit, the conduction reliability between the electrodes can be more effectively enhanced. It is possible to more effectively prevent cracking of the conductive portion due to impact.
  • the content of the above-mentioned phosphorus produces a thin film section of conductive particles using a focused ion beam, and an energy dispersive X-ray using a field emission type transmission electron microscope ("JEM-2010 FEF” manufactured by JEOL Ltd.) It can be measured by an analyzer (EDS).
  • JEM-2010 FEF field emission type transmission electron microscope
  • the thickness of the first conductive portion is preferably 100 nm or more, more preferably 150 nm or more, preferably 300 nm or less, more preferably 250 nm or less. When the thickness of the first conductive portion is greater than or equal to the lower limit and less than or equal to the upper limit, connection resistance between the electrodes is further effectively reduced.
  • the thickness of the first conductive portion means the thickness of the portion where the first conductive portion is formed, and the portion where the first conductive portion is not formed is not included.
  • the thickness of the first conductive portion indicates the average thickness of the first conductive portion in the conductive particle.
  • the thickness of the first conductive portion can be measured, for example, by observing the cross section of the conductive particle using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the conductive particle has a second conductive portion.
  • the second conductive portion preferably contains gold, silver, palladium, platinum, copper, cobalt, ruthenium, indium or tin, more preferably gold or silver, and still more preferably gold.
  • metals that can be used for the second conductive portion include gold, silver, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, palladium, chromium, titanium, antimony, bismuth, thallium Germanium, cadmium, silicon, tungsten, molybdenum and tin-doped indium oxide (ITO).
  • ITO tin-doped indium oxide
  • the second conductive portion is preferably a conductive portion containing gold, and preferably contains gold as a main metal.
  • the content of gold in 100% by weight of the second conductive portion is preferably 10% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, still more preferably 70% by weight or more Preferably it is 90 weight% or more.
  • the content of gold in 100% by weight of the second conductive portion may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more.
  • the ionizing tendency of the metal contained in the first conductive portion is, from the viewpoint of more effectively improving the conduction reliability between the electrodes and the viewpoint of more effectively preventing the cracking of the conductive portion due to external impact, It is preferable that the ionization tendency of the metal contained in the second conductive portion is larger.
  • the thickness of the second conductive portion is preferably 20 nm or more, more preferably 25 nm or more, preferably 40 nm or less, more preferably 35 nm or less.
  • the thickness of the second conductive portion means the thickness of the portion where the second conductive portion is formed, and the portion where the second conductive portion is not formed is not included.
  • the thickness of the second conductive portion indicates the average thickness of the second conductive portion in the conductive particle.
  • the thickness of the second conductive portion can be measured, for example, by observing the cross section of the conductive particle using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the method of forming the first conductive portion and the second conductive portion is not particularly limited.
  • the method of forming the first conductive portion and the second conductive portion includes, for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a metal powder or metal powder and a binder.
  • the method of coating a paste on the surface of a substrate particle, etc. are mentioned.
  • a method by electroless plating is preferred because the formation of the conductive portion is simple.
  • Examples of the method by physical vapor deposition include methods such as vacuum deposition, ion plating and ion sputtering.
  • the following method etc. are mentioned as a method of controlling content of nickel and phosphorus in the said 1st electroconductive part.
  • the method for producing the conductive particles comprises: using conductive particles comprising a base material particle and a first conductive portion disposed on the surface of the base material particle, on the outer surface of the first conductive portion And disposing the second conductive portion by plating. By this step, conductive particles provided with the second conductive portion on the outer surface of the first conductive portion can be obtained.
  • the content of phosphorus on the second conductive portion side in the first conductive portion in the thickness direction of the first conductive portion corresponds to the first conductive portion. It is preferable to make it more than content of the phosphorus at the said base-material particle side in part.
  • the content of phosphorus on the second conductive portion side in the first conductive portion is compared to the content of phosphorus on the base particle side in the first conductive portion
  • a metal for example, nickel or the like
  • replacement gold is used in the plating process for forming the second conductive portion. It is preferable to use plating and reduction gold plating in combination.
  • a metal for example, nickel or the like
  • substitution gold plating and reduction gold plating in combination. It can. As a result, it is possible to more effectively suppress the occurrence of pinholes in the first conductive portion, and it is possible to more effectively prevent cracking of the conductive portion due to an external impact.
  • nickel plating is performed in advance before performing the plating process for forming the second conductive portion.
  • the method to do is mentioned.
  • nickel plating in advance nickel for elution, which is eluted by plating (substituting gold plating and reducing gold plating) to form the second conductive portion, is arranged in advance on the surface of the first conductive portion.
  • the elution nickel is eluted to form a metal (eg, nickel etc.) that is a material of the first conductive portion. Elution can be suppressed. As a result, it is possible to more effectively suppress the occurrence of pinholes in the first conductive portion, and it is possible to more effectively prevent cracking of the conductive portion due to an external impact.
  • the method for producing the conductive particles is to combine the methods described above. Is preferred. Specifically, it is preferable to combine the following (first configuration), (second configuration), and (third configuration).
  • first configuration In the method of manufacturing the conductive particle, the content of phosphorus on the second conductive portion side in the first conductive portion in the thickness direction of the first conductive portion is the first content. The content of phosphorus is made larger than the content of phosphorus on the side of the base particle in the conductive part of (Second Configuration)
  • the plating process for forming the second conductive portion uses both replacement gold plating and reduction gold plating.
  • Nickel plating is performed in advance before performing the plating process for forming the second conductive portion.
  • the outer surface of the second conductive portion is observed with an electron microscope by combining all the configurations described above, there is no pinhole having a dimension of 50 nm or more in the maximum length direction, or the maximum length
  • the second conductive portion can be formed such that a pinhole with a dimension in the longitudinal direction of 50 nm or more is present at 1 / ⁇ m 2 or less.
  • the conductive particles have a plurality of protrusions on the outer surfaces of the first conductive portion and the second conductive portion.
  • the conductive particles have a plurality of projections on the outer surfaces of the first conductive portion and the second conductive portion, whereby the conduction reliability between the electrodes can be further enhanced.
  • An oxide film is often formed on the surface of the electrode connected by the conductive particles.
  • an oxide film is often formed on the surfaces of the first conductive portion and the second conductive portion of the conductive particle.
  • the electrodes and the conductive particles can be more reliably brought into contact, and the connection resistance between the electrodes can be further effectively lowered. Furthermore, when the conductive particles have an insulating substance on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the protrusions of the conductive particles allow the conductive particles and the electrode to be separated. The resin between is effectively eliminated. Therefore, the conduction reliability between the electrodes can be more effectively enhanced.
  • the core material is embedded in the first conductive portion and the second conductive portion to easily form a plurality of protrusions on the outer surfaces of the first conductive portion and the second conductive portion. can do.
  • the core material may not necessarily be used.
  • a method of forming the above-mentioned projection after making a core substance adhere to the surface of substrate particles, a method of forming the 1st electric conduction part and the 2nd electric conduction part by electroless plating, and the surface of substrate particles After forming the first conductive portion by electroless plating, a core material may be attached, and a second conductive portion may be formed by electroless plating.
  • the core material is disposed on the first conductive portion, and then the second conductive portion is formed.
  • a method of adding a core substance in the middle of forming a conductive portion (such as a first conductive portion or a second conductive portion) on the surface of a substrate particle.
  • the first conductive portion is formed on the base material particles by electroless plating without using the above-mentioned core substance, and then plating is deposited in the form of protrusions on the surface of the first conductive portion.
  • a method of forming the second conductive portion by electroless plating may be used.
  • the core substance is added to the dispersion liquid of the substrate particle, and the core substance is added to the surface of the substrate particle, van der Waals force, etc.
  • the core material is added to the container containing the substrate particles, and the core material is attached to the surface of the substrate particles by mechanical action such as rotation of the container. .
  • the material of the core material is not particularly limited.
  • an electroconductive substance and a nonelectroconductive substance are mentioned, for example.
  • the conductive substance include metals, metal oxides, conductive nonmetals such as graphite, and conductive polymers.
  • Examples of the conductive polymer include polyacetylene and the like.
  • Examples of the nonconductive material include silica, alumina, barium titanate and zirconia.
  • the core material is preferably metal because the conductivity can be increased and the connection resistance can be effectively lowered.
  • the core material is preferably metal particles. As a metal which is a material of the said core substance, the metal quoted as a material of the said conductive material can be used suitably.
  • the Mohs hardness of the material of the core material is preferably high.
  • materials having high Mohs hardness barium titanate (Mohs hardness 4.5), nickel (Mohs hardness 5), silica (silicon dioxide, Mohs hardness 6 to 7), titanium oxide (Mohs hardness 7), zirconia (Mohs hardness) 8 to 9), alumina (Mohs hardness 9), tungsten carbide (Mohs hardness 9), diamond (Mohs hardness 10) and the like.
  • the core material is preferably nickel, silica, titanium oxide, zirconia, alumina, tungsten carbide or diamond, and more preferably silica, titanium oxide, zirconia, alumina, tungsten carbide or diamond.
  • the core material is more preferably titanium oxide, zirconia, alumina, tungsten carbide or diamond, and particularly preferably zirconia, alumina, tungsten carbide or diamond.
  • the Mohs hardness of the material of the core material is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, still more preferably 7 or more, particularly preferably 7.5 or more.
  • the shape of the core material is not particularly limited.
  • the shape of the core substance is preferably massive.
  • the core substance may, for example, be a particulate mass, an aggregate in which a plurality of microparticles are aggregated, or an amorphous mass.
  • the 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 electrodes becomes effectively low that the particle diameter of the said core substance is more than the said lower limit and below the said upper limit.
  • the particle size of the core substance indicates a number average particle size.
  • the particle diameter of the core substance is preferably determined by observing 50 arbitrary core substances with an electron microscope or an optical microscope and calculating an average value.
  • the number of the projections per one conductive particle is preferably 3 or more, more preferably 5 or more.
  • the upper limit of the number of projections is not particularly limited.
  • the upper limit of the number of protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles, the use of the conductive particles, and the like.
  • the number of the projections per one conductive particle is preferably determined by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.
  • the height of the plurality of projections is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, and preferably 0.9 ⁇ m or less, more preferably 0.2 ⁇ m or less.
  • the connection resistance between electrodes becomes effective low that the height of the said protrusion is more than the said minimum and below the said upper limit.
  • the conductive particle preferably includes an insulating material disposed on the surface of the conductive portion.
  • an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between adjacent electrodes in the lateral direction rather than between the upper and lower electrodes.
  • the insulating substance between the conductive portion of the conductive particles and the electrodes can be easily removed.
  • the insulating material is preferably insulating particles, because the insulating material can be more easily removed at the time of pressure bonding between the electrodes.
  • the inorganic substance etc. which were mentioned as a material of the resin particle mentioned above, and the material of the base material particle mentioned above are mentioned. It is preferable that the material of the said insulating substance is a material of the resin particle mentioned above.
  • the insulating material is preferably the above-described resin particles or the above-described organic-inorganic hybrid particles, and may be resin particles or organic-inorganic hybrid particles.
  • insulating substance examples include polyolefin compounds, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, cross-linked thermoplastic resins, thermosetting resins and water-soluble materials Resin etc. are mentioned.
  • As the material of the insulating substance only one type may be used, or two or more types may be used in combination.
  • Examples of the above-mentioned polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer and the like.
  • Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polydodecyl (meth) acrylate and polystearyl (meth) acrylate.
  • Examples of the block polymer include polystyrene, styrene-acrylic acid ester copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, hydrogenated products thereof, and the like.
  • thermoplastic resin examples include vinyl polymers and vinyl copolymers. An epoxy resin, a phenol resin, a melamine resin etc. are mentioned as said thermosetting resin.
  • thermosetting resin examples include polyethylene glycol methacrylate, alkoxylated trimethylolpropane methacrylate, alkoxylated pentaerythritol methacrylate, and the like.
  • water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide and methyl cellulose.
  • a chain transfer agent may be used to adjust the degree of polymerization. Examples of chain transfer agents include thiol and carbon tetrachloride.
  • a chemical method As a method of disposing the insulating material on the surface of the conductive part (second conductive part), a chemical method, a physical or mechanical method, etc. may be mentioned.
  • 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 deposition, spraying, dipping and vacuum deposition.
  • a method of disposing the insulating material on the surface of the second conductive portion via a chemical bond is preferable because the insulating material is hardly released.
  • the outer surface of the conductive part (second conductive part) and the surface of the insulating material may be coated with a compound having a reactive functional group.
  • the outer surface of the conductive portion (second conductive portion) and the surface of the insulating material 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 the functional group on the surface of the insulating substance through a polymer electrolyte such as polyethyleneimine. Absent.
  • the particle diameter of the insulating material can be appropriately selected depending on the particle diameter of the conductive particles, the use of the conductive particles, and the like.
  • the particle diameter of the insulating material is preferably 10 nm or more, more preferably 100 nm or more, preferably 4000 nm or less, more preferably 2000 nm or less.
  • the particle diameter of the insulating material is equal to or more than the above lower limit, when the conductive particles are dispersed in the binder resin, the conductive portions in the plurality of conductive particles do not easily contact each other.
  • the particle size of the insulating material is not more than the above upper limit, there is no need to make the pressure too high in order to eliminate the insulating material between the electrode and the conductive particles when connecting the electrodes. There is no need to heat to a high temperature.
  • the particle size of the insulating material indicates a number average particle size.
  • the particle diameter of the insulating material can be determined using a particle size distribution measuring device or the like.
  • the particle diameter of the insulating material is preferably determined by observing 50 arbitrary insulating materials with an electron microscope or an optical microscope and calculating an average value. In the case of measuring the particle size of the insulating material in the conductive particles, it can be measured, for example, as follows.
  • the conductive particles are added to “Technobit 4000” manufactured by Kulzer Co. so that the content is 30% by weight, and dispersed to prepare a conductive particle inspection embedded resin.
  • the cross section of the conductive particles is cut out using an ion milling apparatus ("IM 4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the dispersed conductive particles in the embedded resin for inspection.
  • IM 4000 manufactured by Hitachi High-Technologies Corporation
  • FE-SEM field emission scanning electron microscope
  • the image magnification is set to 50,000 times, 50 conductive particles are randomly selected, and the insulating material of each conductive particle is observed. Do.
  • the particle size of the insulating material in each conductive particle is measured, and arithmetic mean of them is used as the particle size of the insulating material.
  • the conductive material according to the present invention includes the above-described conductive particles and a binder resin.
  • the conductive particles are preferably dispersed in a binder resin and used, and preferably dispersed in a binder resin and used as a conductive material.
  • the conductive material is preferably an anisotropic conductive material.
  • the conductive material is preferably used for electrical connection between the electrodes.
  • the conductive material is preferably a conductive material for circuit connection.
  • the binder resin is not particularly limited.
  • a well-known insulating resin is used as said binder resin.
  • the binder resin preferably contains a thermoplastic component (thermoplastic compound) or a curable component, and more preferably contains a curable component.
  • a photocurable component and a thermosetting component are mentioned. It is preferable that the said photocurable component contains a photocurable compound and a photoinitiator. It is preferable that the said thermosetting component contains a thermosetting compound and a thermosetting agent.
  • binder resin a vinyl resin, a thermoplastic resin, curable resin, a thermoplastic block copolymer, an elastomer, etc. are mentioned, for example.
  • the binder resin may be used alone or in combination of two or more.
  • 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.
  • As said curable resin an epoxy resin, a urethane resin, a polyimide resin, unsaturated polyester resin etc. are mentioned, for example.
  • the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin.
  • the curable resin may be used in combination with a curing agent.
  • thermoplastic block copolymer examples include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated substance of styrene-butadiene-styrene block copolymer, and styrene-isoprene. -Hydrogenated products of styrene block copolymer and the like can be mentioned.
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • the conductive 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 light stability.
  • Various additives such as agents, UV absorbers, lubricants, antistatic agents and flame retardants may be included.
  • the viscosity ((25) at 25 ° C. of the conductive material is preferably 20 Pa. ⁇ S or more, more preferably 30 Pa ⁇ s or more, preferably 400 Pa ⁇ s or less, more preferably 300 Pa ⁇ s or less.
  • the viscosity ( ⁇ 25) can be appropriately adjusted according to the type and the amount of the blending component.
  • the viscosity can be measured, for example, using an E-type viscometer ("TVE 22L” manufactured by Toki Sangyo Co., Ltd.) under conditions of 25 ° C. and 5 rpm.
  • E-type viscometer (“TVE 22L” manufactured by Toki Sangyo Co., Ltd.) under conditions of 25 ° C. and 5 rpm.
  • the said conductive material can be used as a conductive paste, a conductive film, etc.
  • the conductive material is a conductive film
  • a film not containing conductive particles may be laminated on a conductive film containing conductive particles.
  • the conductive paste is preferably an anisotropic conductive paste.
  • the conductive film is preferably an anisotropic conductive film.
  • the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, based on 100% by weight of the conductive material. Is 99.99% by weight or less, more preferably 99.9% by weight or less.
  • the content of the binder resin is the lower limit or more and the upper limit or less, the conductive particles are efficiently disposed between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further enhanced. .
  • the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and preferably 80% by weight or less, more preferably 60% by weight in 100% by weight of the conductive material. % Or less, more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less.
  • the content of the conductive particles is not less than the lower limit and not more than the upper limit, the conduction reliability between the electrodes is further enhanced.
  • connection structure can be obtained by connecting members to be connected using the conductive particles or a conductive material containing the conductive particles and a binder resin.
  • the connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member.
  • the material is preferably the above-described conductive particles, or a conductive material containing the above-described conductive particles and a binder resin. It is preferable that the connection portion be formed of the above-described conductive particles, or be formed of a conductive material containing the above-described conductive particles and a binder resin. When the conductive particles are used, the connection portion itself is the conductive particles.
  • the first connection target member preferably has a first electrode on the surface.
  • the second connection target member preferably has a second electrode on the surface. It is preferable that the first electrode and the second electrode be electrically connected by the conductive particles.
  • connection structure preferably includes a flexible member as the first connection target member or the second connection target member.
  • first connection target member and the second connection target member may be a flexible member, and both the first connection target member and the second connection target member may be flexible members. It may be It is preferable that the connection structure is used in a state where the flexible member is curved. It is preferable that the connection structure is used in a state where the connection portion is curved.
  • FIG. 3 is sectional drawing which shows typically the bonded structure using the electroconductive particle which concerns on the 1st Embodiment of this invention.
  • connection structure 51 shown in FIG. 3 is a connection portion connecting the first connection target member 52, the second connection target member 53, the first connection target member 52, and the second connection target member 53. And 54.
  • the connection portion 54 is formed of a conductive material including the conductive particle 1. It is preferable that the conductive material has a thermosetting property, and the connection portion 54 be formed by thermosetting the conductive material.
  • the conductive particles 1 are schematically illustrated for the convenience of illustration. Instead of the conductive particles 1, conductive particles 21 or the like may be used.
  • the first connection target member 52 has a plurality of first electrodes 52 a on the surface (upper surface).
  • the second connection target member 53 has a plurality of second electrodes 53a on the front surface (lower surface).
  • the first electrode 52 a and the second electrode 53 a are electrically connected by one or more conductive particles 1. Therefore, the first connection target member 52 and the second connection target member 53 are electrically connected by the conductive particles 1.
  • the manufacturing method of the said connection structure is not specifically limited.
  • the conductive material is disposed between the first connection target member and the second connection target member, and after obtaining the laminate, the laminate is heated and pressed. Methods etc.
  • the pressure of the thermocompression bonding is about 0.5 ⁇ 10 6 Pa to 5 ⁇ 10 6 Pa with respect to the area to be crimped.
  • the heating temperature of the thermocompression bonding is about 70 ° C. to 230 ° C.
  • the heating temperature of the thermocompression bonding is preferably 80 ° C. or more, more preferably 100 ° C. or more, preferably 200 ° C. or less, more preferably 150 ° C. or less.
  • the pressure of the thermocompression bonding is preferably 0.5 ⁇ 10 6 Pa or more, more preferably 1 ⁇ 10 6 Pa or more, preferably 5 ⁇ 10 6 Pa or less, more preferably 3 ⁇ 10 6 Pa or less .
  • the pressure and temperature of the thermocompression bonding are equal to or higher than the lower limit and lower than the upper limit, the conduction reliability between the electrodes can be more effectively enhanced.
  • connection target member examples include electronic components such as a semiconductor chip, a capacitor, and a diode, and electronic components such as a printed circuit board, a flexible printed circuit, a circuit board such as a glass epoxy substrate and a glass substrate, and the like.
  • the connection target member is preferably an electronic component. It is preferable that the said electroconductive particle is used for the electrical connection of the electrode in an electronic component.
  • connection object member metal electrodes, such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a silver electrode, a SUS electrode, a copper electrode, a molybdenum electrode, a tungsten electrode, etc. are mentioned.
  • 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 indium oxide in which the trivalent metal element was doped, the zinc oxide in which the trivalent metal element was doped, etc. are mentioned. Sn, Al, Ga, etc. are mentioned as said trivalent metal element.
  • Base particle Base particle A: resin particle, copolymer resin particle of divinyl benzene and isobornyl acrylate, particle diameter: 10 ⁇ m
  • Base particle B resin particle, copolymer resin particle of divinyl benzene and isobornyl acrylate, particle diameter: 5 ⁇ m
  • Base particle C resin particle, copolymer resin particle of divinyl benzene and isobornyl acrylate, particle diameter: 20 ⁇ m
  • Example 1 Formation of first conductive portion (nickel layer) After dispersing 10 parts by weight of the substrate particles A in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, the solution The base material particle A was taken out by filtering the Subsequently, the substrate particle A was added to 100 parts by weight of a 1% by weight solution of dimethylamine borane to activate the surface of the substrate particle A. After thoroughly washing the surface-activated substrate particles A, they were added to 500 parts by weight of distilled water and dispersed to obtain a suspension.
  • a nickel plating solution (pH 9.0) containing 0.25 mol / L of nickel sulfate, 0.25 mol / L of sodium hypophosphite and 0.15 mol / L of sodium citrate was prepared.
  • the above-mentioned nickel plating solution was gradually dropped to the suspension to carry out electroless nickel plating. Thereafter, the suspension is filtered to take out the particles, washed with water, and dried to obtain particles in which the first conductive portion (nickel-phosphorus layer, 200 nm thick) is disposed on the surface of the substrate particle A. Obtained.
  • the content of nickel in 100% by weight of the conductive layer was 94.5% by weight, and the content of phosphorus was 5.5% by weight.
  • Example 2 Formation of first conductive portion (nickel layer) After dispersing 10 parts by weight of the base particle B in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, the solution The base material particle B was taken out by filtering the Subsequently, the substrate particle B was added to 100 parts by weight of a 1 wt% solution of dimethylamine borane to activate the surface of the substrate particle B. After thoroughly washing the surface-activated substrate particles B, they were added to 500 parts by weight of distilled water and dispersed to obtain a suspension.
  • a nickel plating solution (pH 9.0) containing 0.25 mol / L of nickel sulfate, 0.25 mol / L of sodium hypophosphite and 0.15 mol / L of sodium citrate was prepared.
  • the above-mentioned nickel plating solution was gradually dropped to the suspension to carry out electroless nickel plating. Thereafter, the suspension is filtered to take out the particles, washed with water, and dried to obtain particles in which the first conductive portion (nickel-phosphorus layer, thickness 210 nm) is disposed on the surface of the base particle B. Obtained.
  • the content of nickel in 100% by weight of the conductive layer was 94.5% by weight, and the content of phosphorus was 5.5% by weight.
  • second conductive portion 10 parts by weight of particles in which the first conductive portion and the nickel plating layer are disposed on the surface of the base material particle B are added to 100 parts by weight of distilled water and dispersed The suspension gave a suspension.
  • a reduced gold plating solution containing 0.03 mol / L of gold cyanide and 0.1 mol / L of hydroquinone as a reducing agent was prepared. While stirring the obtained suspension at 70 ° C., the above reduced gold plating solution was gradually dropped to the suspension to carry out reduced gold plating. Thereafter, the suspension was filtered to take out the particles, washed with water, and dried to obtain conductive particles.
  • the second conductive portion gold layer, thickness 30 nm
  • Example 3 In the same manner as in Example 2, except that the base particle B was changed to the base particle C and the thickness of the second conductive portion was changed to 35 nm when forming the first conductive portion, Conductive particles were obtained. In the obtained conductive particles, the second conductive portion (gold layer, thickness 35 nm) was disposed on the outer surface of the first conductive portion.
  • Example 4 When forming the first conductive portion, the substrate particle B is changed to the substrate particle A, and 1 weight part of metal nickel particles (average particle diameter 150 nm) is added to the obtained suspension to obtain a core Conductive particles were obtained in the same manner as Example 2, except that the suspension containing the substrate particle A to which the substance was attached was used, and the thickness of the second conductive portion was changed to 29 nm. In the obtained conductive particles, the second conductive portion (gold layer, thickness 29 nm) was disposed on the outer surface of the first conductive portion. The obtained conductive particles had a plurality of protrusions on the outer surfaces of the first conductive portion and the second conductive portion.
  • Example 5 In forming the second conductive portion, the base particle B was changed to the base particle A, the thickness of the first conductive portion was changed to 230 nm, and cyanide 0.03 mol / L gold cyanide was formed. Conductive particles were obtained in the same manner as in Example 2, except that the gold content was changed to 0.015 mol / L and the thickness of the second conductive portion was changed to 15 nm. In the obtained conductive particles, the second conductive portion (gold layer, 15 nm thick) was disposed on the outer surface of the first conductive portion.
  • Example 6 In the same manner as in Example 1, except that gold cyanide was changed to palladium sulfate and the thickness of the second conductive portion was changed to 30 nm when forming the second conductive portion, conductive particles were obtained. I got In the obtained conductive particles, the second conductive portion (palladium layer, thickness 30 nm) was disposed on the outer surface of the first conductive portion.
  • Example 7 In the same manner as in Example 2, except that the base particle B was changed to the base particle A and the thickness of the second conductive portion was changed to 32 nm when forming the first conductive portion, Conductive particles were obtained. In the obtained conductive particles, the second conductive portion (gold layer, thickness 32 nm) was disposed on the outer surface of the first conductive portion.
  • Example 1 A substituted gold plating solution not containing hydroquinone as a reducing agent was prepared.
  • the reduction gold plating solution is changed to a replacement gold plating solution to form a second conductive portion by substitution gold plating instead of reduction gold plating, and Conductive particles were obtained in the same manner as in Example 1 except that the thickness of the conductive portion was changed to 32 nm.
  • the second conductive portion gold layer, thickness 32 nm
  • the image of the surface of the electroconductive particle produced by the comparative example 1 was shown in FIG.
  • the number of first pinholes whose dimension in the maximum longitudinal direction per 1 ⁇ m 2 was 50 nm or more was measured.
  • measure the number of second pinholes with a dimension of 50 nm to 200 nm in the maximum length direction per 1 ⁇ m 2 did.
  • the average particle size of the obtained conductive particles was measured using a “laser diffraction type particle size distribution measuring apparatus” manufactured by Horiba, Ltd. In addition, the average particle size of the conductive particles was calculated by averaging the measurement results of 20 times.
  • the crack of the conductive portion was evaluated using the obtained conductive particles.
  • the cracking of the conductive part was evaluated as follows. The cracking of the conductive part was determined according to the following criteria.
  • Evaluation method of cracking of conductive part A photograph of 1000 conductive particles was taken using an electron microscope at a magnification which reflects about 100 conductive particles per sheet. The photograph of the obtained 1000 conductive particles was observed, and the number of conductive particles in which a crack having a length of half or more of the diameter of the conductive particles was present was measured.
  • ⁇ The number of conductive particles having a crack is less than 100.
  • ⁇ The number of conductive particles having a crack is 100 or more.
  • connection structure X The obtained conductive particles were added to “Structbond XN-5A” manufactured by Mitsui Chemicals, Inc. so as to have a content of 10% by weight, and dispersed to prepare an anisotropic conductive paste.
  • a transparent glass substrate having an ITO electrode pattern with L / S of 20 ⁇ m / 20 ⁇ m on the top was prepared.
  • a semiconductor chip having a gold electrode pattern with L / S of 20 ⁇ m / 20 ⁇ m on the lower surface was prepared.
  • an anisotropic conductive paste immediately after preparation was applied to a thickness of 30 ⁇ m to form an anisotropic conductive paste layer.
  • the said semiconductor chip was laminated
  • the pressure heating head is placed on the upper surface of the semiconductor chip, and a low pressure of 1 MPa calculated from the crimp area is applied.
  • the anisotropic conductive paste layer was cured at 100 ° C. to obtain a connection structure X.
  • connection Structure Y A bonded structure Y was produced in the same manner as the bonded structure X except that the temperature at the time of curing the anisotropic conductive material layer was changed to 150 ° C.
  • connection Structure Z A bonded structure Z was produced in the same manner as the bonded structure X except that the temperature at the time of curing the anisotropic conductive material layer was changed to 200 ° C.
  • Connection resistance A is 2.0 ⁇ or less ⁇ ⁇ : Connection resistance A exceeds 2.0 ⁇ to 3.0 ⁇ or less ⁇ : Connection resistance A exceeds 3.0 ⁇ to 5.0 ⁇ or less ⁇ : Connection resistance A is 5 .0 ⁇ to 10 ⁇ or less ⁇ : Connection resistance A exceeds 10 ⁇
  • connection resistance after high temperature and high humidity (conduction reliability)
  • the connection structures X, Y and Z after evaluation of the connection resistance in the above (7) initial stage were left for 500 hours under the conditions of 85 ° C. and 85% humidity.
  • the connection resistances B between the upper and lower electrodes of the connection structures X, Y, and Z after being left for 500 hours were each measured by the four-terminal method.
  • the connection resistance (conduction reliability) after being left at high temperature and high humidity was determined from the connection resistances A and B according to the following criteria.
  • connection resistance B is less than 1.25 times connection resistance A
  • connection resistance B is 1.25 times or more and less than 1.5 times connection resistance A
  • connection resistance B is 1. of connection resistance A 5 times or more and 2 times or less
  • connection resistance B is 2 times or more and 5 times or less of connection resistance A
  • connection resistance B is 5 times or more of connection resistance A

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PCT/JP2018/023660 2017-06-22 2018-06-21 導電性粒子、導電性粒子の製造方法、導電材料及び接続構造体 WO2018235909A1 (ja)

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CN201880030129.3A CN110603612B (zh) 2017-06-22 2018-06-21 导电性粒子、导电性粒子的制造方法、导电材料以及连接结构体
CN202210997623.5A CN115458206A (zh) 2017-06-22 2018-06-21 导电性粒子、导电性粒子的制造方法、导电材料以及连接结构体
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JP5719483B1 (ja) * 2013-09-12 2015-05-20 積水化学工業株式会社 導電性粒子、導電材料及び接続構造体
JP6641164B2 (ja) * 2014-12-04 2020-02-05 積水化学工業株式会社 基材粒子、導電性粒子、導電材料及び接続構造体

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JP2014132542A (ja) * 2012-01-11 2014-07-17 Hitachi Chemical Co Ltd 導電粒子、絶縁被覆導電粒子及び異方導電性接着剤
JP2014241280A (ja) * 2013-05-14 2014-12-25 積水化学工業株式会社 導電性粒子、導電材料及び接続構造体
JP2015160958A (ja) * 2014-02-26 2015-09-07 日立金属株式会社 導電性粒子、導電性粉体、導電性高分子組成物および異方性導電シート
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JP2016015312A (ja) * 2014-06-11 2016-01-28 積水化学工業株式会社 導電性粒子、導電性粒子の製造方法、導電材料及び接続構造体

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