WO2011111152A1 - Electroconductive particle, anisotropic electroconductive material and connecting structure - Google Patents

Electroconductive particle, anisotropic electroconductive material and connecting structure Download PDF

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Publication number
WO2011111152A1
WO2011111152A1 PCT/JP2010/053786 JP2010053786W WO2011111152A1 WO 2011111152 A1 WO2011111152 A1 WO 2011111152A1 JP 2010053786 W JP2010053786 W JP 2010053786W WO 2011111152 A1 WO2011111152 A1 WO 2011111152A1
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WIPO (PCT)
Prior art keywords
palladium
nickel
particles
layer
conductive particles
Prior art date
Application number
PCT/JP2010/053786
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French (fr)
Japanese (ja)
Inventor
暁舸 王
Original Assignee
積水化学工業株式会社
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Publication date
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 KR1020127023400A priority Critical patent/KR101704856B1/en
Priority to PCT/JP2010/053786 priority patent/WO2011111152A1/en
Publication of WO2011111152A1 publication Critical patent/WO2011111152A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
    • H—ELECTRICITY
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    • 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
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
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Definitions

  • the present invention relates to conductive particles that can be used for connection between electrodes, and more specifically, conductive particles that can improve connection reliability between electrodes when used for connection between electrodes, and the conductive property.
  • the present invention relates to an anisotropic conductive material using particles and a connection structure.
  • Anisotropic conductive materials such as anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, anisotropic conductive film, or anisotropic conductive sheet are widely known.
  • anisotropic conductive materials conductive particles are dispersed in paste, ink, or resin.
  • the anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, connection between an IC chip and a circuit board having an ITO electrode, and the like.
  • connection between an IC chip and a circuit board having an ITO electrode and the like.
  • these electrodes can be connected by heating and pressurizing.
  • Patent Document 1 discloses base material particles, a nickel layer formed on the surface of the base material particle, and formed on the surface of the nickel layer. Disclosed is a conductive particle comprising a modified palladium layer.
  • connection structure is formed using the conductive particles described in Patent Document 1 for connection between the electrodes, the connection resistance between the electrodes becomes high when the connection structure is exposed to high temperature and high humidity. Sometimes.
  • An object of the present invention is to form a connection structure by connecting electrodes, and even when the connection structure is exposed to high temperature and high humidity, the conductive particles that do not easily increase the connection resistance between the electrodes, and the An anisotropic conductive material using a conductive particle and a connection structure are provided.
  • base particles there are provided base particles, a nickel layer formed on the surface of the base particles, and a palladium layer formed on the surface of the nickel layer.
  • conductive particles having a palladium content of 5 to 15% by weight and a palladium content of the palladium layer of 96% by weight or more.
  • the conductive particles have protrusions on the surface. In another specific aspect of the present invention, the conductive particles have protrusions on the outer surface of the palladium layer.
  • an insulating resin attached to the surface of the palladium layer is further provided.
  • the insulating resin is an insulating resin particle.
  • the anisotropic conductive material according to the present invention includes conductive particles configured according to the present invention and a binder resin.
  • connection structure includes a first connection target member, a second connection target member, and a connection part that electrically connects the first and second connection target members.
  • the connecting portion is made of the conductive particles of the present invention or an anisotropic conductive material containing the conductive particles and a binder resin.
  • the conductive particles according to the present invention a nickel layer and a palladium layer are formed in this order on the surface of the base particle, the phosphorus content of the nickel layer is in the range of 5 to 15% by weight, and Since the palladium content in the palladium layer is 96% by weight or more, it prevents the connection resistance from increasing when a connection structure using conductive particles for connection between electrodes is exposed to high temperature and high humidity. it can. Therefore, the connection reliability of the connection structure can be improved.
  • FIG. 1 is a cross-sectional view showing conductive particles according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing conductive particles according to another embodiment of the present invention.
  • FIG. 3 is a front sectional view schematically showing a connection structure using conductive particles according to an embodiment of the present invention.
  • FIG. 4 is a plan view for explaining the shape of the comb-shaped electrode copper pattern on the substrate used in the evaluation of the insulation resistance of the example and the comparative example.
  • FIG. 1 is a cross-sectional view showing conductive particles according to an embodiment of the present invention.
  • the conductive particles 1 include a base particle 2, a nickel layer 3 formed on the surface 2 a of the base particle 2, and a palladium layer 4 formed on the surface 3 a of the nickel layer 3. With.
  • the conductive particles 1 may further include an insulating resin attached to the surface 4 a of the palladium layer 4.
  • FIG. 2 is a cross-sectional view showing conductive particles according to another embodiment of the present invention.
  • the conductive particles 21 include base material particles 2, a nickel layer 22 formed on the surface 2 a of the base material particle 2, and a palladium layer 23 formed on the surface 22 a of the nickel layer 22.
  • the nickel layer 22 and the palladium layer 23 are metal layers.
  • the conductive particle 21 includes a plurality of core substances 24 on the surface 2 a of the base particle 2.
  • the nickel layer 22 and the palladium layer 23 that are metal layers cover the core substance 24.
  • the conductive particles 21 have a plurality of protrusions 25 on the surface 21a.
  • the conductive particle 21 has a plurality of protrusions 25 on the outer surface 23 a of the palladium layer 23.
  • the protrusion 25 is formed on the surface 23a of the palladium layer 23 outside the metal layer.
  • a surface 23 a of the palladium layer 23 is raised by the core material 24, and a protrusion 25 is formed.
  • the conductive particles 21 include an insulating resin 26 attached to the surface 23 a of the palladium layer 23.
  • the surface of the palladium layer 23 is covered with an insulating resin 26.
  • the insulating resin 26 is insulating resin particles.
  • the conductive particles may include an insulating resin 26 that covers the surface 23a of the palladium layer 23.
  • the insulating resin 26 is not necessarily provided.
  • Examples of the base particle 2 include resin particles, inorganic particles, organic-inorganic hybrid particles, and metal particles.
  • Examples of the resin for forming the resin particles include divinylbenzene resin, styrene resin, acrylic resin, urea resin, imide resin, phenol resin, polyester resin, and vinyl chloride resin.
  • Examples of the inorganic material for forming the inorganic particles include silica or carbon black.
  • Examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
  • Examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium.
  • the average particle diameter of the base particle 2 is preferably in the range of 1 to 100 ⁇ m.
  • the average particle diameter of the substrate particles is smaller than 1 ⁇ m, the connection reliability between the electrodes may be lowered.
  • the average particle diameter of the substrate particles is larger than 100 ⁇ m, the distance between the electrodes may be too large.
  • the content of phosphorus in the nickel layers 3 and 22 formed on the surface 2a of the base particle 2 is in the range of 5 to 15% by weight.
  • the connection resistance increases when the connection structure using the conductive particles for connection between the electrodes is exposed to high temperature and high humidity.
  • the phosphorus content exceeds 15% by weight, the initial connection resistance of the connection structure using the conductive particles for connection between the electrodes becomes high.
  • the content of phosphorus in the nickel layers 3 and 22 is 5 to 15% by weight, it becomes easy to obtain fine nickel crystals, and it becomes easy to obtain fine palladium crystals by epitaxial growth of palladium plating. For this reason, the connection reliability of the connection structure under high temperature and high humidity can be improved.
  • the phosphorus content in the nickel layers 3 and 22 is preferably in the range of 10 to 15% by weight.
  • the content of phosphorus in the nickel layers 3 and 22 is in the range of 10 to 15% by weight, the connection reliability of the connection structure under high temperature and high humidity can be further improved.
  • a method of bringing the phosphorus content of the nickel layers 3 and 22 into the above range for example, a method of controlling the pH of a nickel plating solution when forming a nickel layer by electroless nickel plating, or electroless nickel plating
  • a method of controlling the concentration of the phosphorus-containing reducing agent when forming the nickel layer by the method described above for example, a method of controlling the concentration of the phosphorus-containing reducing agent when forming the nickel layer by the method described above.
  • the method for measuring the phosphorus content of the nickel layer is not particularly limited.
  • a thin film section of the obtained conductive particles is prepared using a focused ion beam, and a transmission electron microscope FE-TEM (Japan)
  • EDS energy dispersive X-ray analyzer
  • the palladium content of the palladium layers 4 and 23 formed on the surfaces 3a and 22a of the nickel layers 3 and 22 is 96% by weight or more.
  • the palladium content is preferably 98% by weight or more.
  • Examples of a method for making the palladium content of the palladium layers 4 and 23 96% by weight or more include a method of controlling the pH of the palladium plating solution when forming a palladium layer by electroless palladium plating, or electroless palladium.
  • a method of controlling the concentration of the reducing agent when forming the palladium layer by plating may be used.
  • the method for measuring the palladium content in the palladium layer is not particularly limited.
  • a thin film slice of the obtained conductive particles is prepared using a focused ion beam, and a transmission electron microscope FE-TEM (Japan)
  • EDS energy dispersive X-ray analyzer
  • the total thickness of the metal layers of the nickel layers 3 and 22 and the palladium layers 4 and 23 is preferably in the range of 5 to 500 nm, and more preferably in the range of 10 to 400 nm.
  • the thickness of the metal layer is less than 5 nm, the conductivity of the conductive particles may be insufficient.
  • the thickness of the metal layer exceeds 500 nm, the difference in coefficient of thermal expansion between the base particle and the metal layer becomes large, and the metal layer may easily peel from the base particle.
  • Examples of the method of forming the nickel layers 3 and 22 on the surface 2a of the base particle 2 include a method of forming a nickel layer by electroless plating or a method of forming a nickel layer by electroplating.
  • examples of the method of forming the palladium layers 4 and 23 on the surfaces 3a and 22a of the nickel layers 3 and 22 include a method of forming a palladium layer by electroless plating or a method of forming a palladium layer by electroplating.
  • the conductive particles preferably have protrusions on the surface.
  • the conductive particles preferably have protrusions on the surface of the metal layer, and further preferably have protrusions on the surfaces 4a and 23a of the palladium layers 4 and 23.
  • the conductive particles preferably have a plurality of protrusions on the surface.
  • the conductive particles preferably have a plurality of protrusions on the surface of the metal layer, and more preferably have a plurality of protrusions on the surfaces 4 a and 23 a of the palladium layers 4 and 23. In these cases, since the resin between the conductive particles and the electrodes can be effectively eliminated, the connection reliability of the connection structure using the conductive particles for the connection between the electrodes can be improved.
  • a method of forming protrusions on the surface of the conductive particles a method of forming a metal layer by electroless plating after attaching a core substance to the surface of the base particles, or by electroless plating on the surface of the base particles Examples include a method of forming a metal layer by electroless plating after a core layer is adhered after forming the metal layer.
  • a method of attaching the core substance to the surface of the base particle for example, a conductive substance that becomes 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, a fan.
  • a method of accumulating and adhering the core substance on the surface of the base particle in the dispersion is preferable because the amount of the core substance to be attached is easy to control.
  • Examples of the conductive substance constituting the core substance include metals, metal oxides, conductive nonmetals such as graphite, and conductive polymers.
  • Examples of the conductive polymer include polyacetylene. Among them, metal is preferable because conductivity can be increased.
  • the metal examples include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead.
  • examples thereof include alloys composed of two or more metals such as alloys, tin-copper alloys, tin-silver alloys, and tin-lead-silver alloys. Of these, nickel, copper, silver or gold is preferable.
  • the metal constituting the core material may be the same as or different from the metal constituting the metal layer.
  • 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 obtained by aggregating a plurality of fine particles, and an irregular lump.
  • the conductive particles according to the present invention preferably further include an insulating resin attached to the surface of the palladium layer.
  • an insulating resin attached to the surface of the palladium layer.
  • the insulating resin include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked thermoplastic resins, thermosetting resins or water-soluble resins. Etc.
  • thermoplastic resin examples include vinyl polymers and vinyl copolymers.
  • thermosetting resin examples include an epoxy resin, a phenol resin, and a melamine resin.
  • 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 chemical method As a method for attaching an insulating resin to the surface of the palladium layer, a chemical method, a physical or mechanical method, and the like can be given.
  • the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, or an emulsion polymerization method.
  • the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spraying, dipping, or vacuum deposition.
  • the insulating resin is preferably insulating resin particles.
  • the conductive particles when used for connection between the electrodes, not only can a short circuit between adjacent electrodes be prevented, but also the connection resistance between the opposing electrodes can be reduced.
  • a chemical method As a method for attaching the insulating resin particles to the surface of the palladium layer, a chemical method, a physical or mechanical method, and the like can be given.
  • the chemical method include a method of attaching insulating resin particles to the surface of the palladium layer through a chemical bond.
  • the physical or mechanical method include a method using hybridization or an electrostatic adhesion method.
  • a method of attaching the insulating resin particles to the surface of the palladium layer through a chemical bond is preferable.
  • the anisotropic conductive material according to the present invention contains the conductive particles of the present invention and a binder resin.
  • the binder resin is not particularly limited.
  • As the binder resin generally an insulating resin is used.
  • Examples of the binder resin include a vinyl resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer, or an elastomer.
  • binder 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, polyamide resin, and the like.
  • examples of the curable resin include epoxy resins, urethane resins, polyimide resins, and unsaturated polyester resins.
  • 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 a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, or a styrene-isoprene. -Hydrogenated products of styrene block copolymers.
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • Anisotropic conductive materials include, for example, fillers, extenders, softeners, plasticizers, polymerization catalysts, curing catalysts, colorants, antioxidants, thermal stabilizers, light stabilizers, in addition to conductive particles and binder resins.
  • Various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent or a flame retardant may be contained.
  • the method for dispersing the conductive particles in the binder resin may be any conventionally known dispersion method and is not particularly limited.
  • Examples of the method for dispersing the conductive particles in the binder resin include, for example, a method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like.
  • the conductive particles are dispersed in water or an organic solvent. After uniformly dispersing using a homogenizer or the like, it is added to a binder resin and kneaded with a planetary mixer or the like, or after the binder resin is diluted with water or an organic solvent, the conductive particles are dispersed.
  • mixing with a planetary mixer etc., and dispersing is mentioned.
  • the anisotropic conductive material of the present invention can be used as an anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, anisotropic conductive film, anisotropic conductive sheet or the like.
  • anisotropic conductive material containing the conductive particles of the present invention is used as a film-like adhesive such as an anisotropic conductive film or an anisotropic conductive sheet, the film-like shape containing the conductive particles is used.
  • a film-like adhesive that does not contain conductive particles may be laminated on the adhesive.
  • FIG. 3 is a front sectional view showing a connection structure using conductive particles according to an embodiment of the present invention.
  • connection structure 11 includes a circuit board 12 as a first connection target member, a semiconductor chip 14 as a second connection target member, and electrodes of the circuit board 12 and the semiconductor chip 14. 12a, and 14a are provided with the connection part 13 which has connected electrically.
  • the connection part 13 is formed of an anisotropic conductive film.
  • a plurality of electrodes 12 a are provided on the upper surface of the circuit board 12.
  • a plurality of electrodes 14 a are provided on the lower surface of the semiconductor chip 14.
  • a semiconductor chip 14 is laminated on the upper surface of the circuit board 12 via an anisotropic conductive film containing the conductive particles 1.
  • a connecting portion 13 formed of an anisotropic conductive film including the conductive particles 1 is disposed between the electrode 12a and the electrode 14a.
  • conductive particles 21 may be used. In FIG. 3, the conductive particles 1 are shown schematically.
  • connection structure an electronic component chip such as a semiconductor chip, a capacitor chip or a diode chip is mounted on a circuit board, and the electrode of the electronic component chip is connected to an electrode on the circuit board.
  • Examples include electrically connected structures.
  • a circuit board various printed circuit boards, such as various printed circuit boards, such as a flexible printed circuit board, a glass substrate, or a board
  • connection structure is not particularly limited.
  • the anisotropic conductive material is provided between a first connection target member such as an electronic component or a circuit board and a second connection target member such as an electronic component or a circuit board.
  • a method of heating and pressurizing the laminated body after arranging and obtaining the laminated body is mentioned.
  • Example 1 Electroless nickel plating step Divinylbenzene resin particles having an average particle diameter of 4 ⁇ m were treated with a 10 wt% solution of an ion adsorbent for 5 minutes, and then treated with a 0.01 wt% palladium sulfate aqueous solution for 5 minutes. Thereafter, dimethylamine borane was added for reduction treatment, filtration, and washing to obtain resin particles to which palladium was attached.
  • a 1% by weight sodium succinate solution in which sodium succinate was dissolved in 500 mL of ion-exchanged water was prepared.
  • 10 g of resin particles with palladium attached were added and mixed to prepare a slurry.
  • the pH of the slurry was adjusted to 6.5.
  • As a nickel plating solution an initial nickel solution containing 10% by weight of nickel sulfate, 10% by weight of sodium hypophosphite, 4% by weight of sodium hydroxide and 20% by weight of sodium succinate was prepared.
  • the slurry adjusted to pH 6.5 was heated to 80 ° C., and then the nickel solution was continuously added dropwise to the slurry and stirred for 20 minutes to advance the plating reaction. After confirming that hydrogen was no longer generated, the plating reaction was completed.
  • a late nickel solution containing 20% by weight of nickel sulfate, 20% by weight of sodium hypophosphite and 5% by weight of sodium hydroxide was prepared.
  • the late nickel solution was continuously added dropwise to the solution that had undergone the plating reaction with the nickel solution, and the plating reaction was allowed to proceed by stirring for 1 hour. In this way, a nickel layer was formed on the surface of the resin particles to obtain nickel plated particles.
  • the nickel layer had a thickness of 0.1 ⁇ m.
  • Electroless palladium plating step 10 g of the obtained nickel-plated particles were dispersed in 500 mL of ion-exchanged water using an ultrasonic treatment machine to obtain a particle suspension. While stirring the suspension at 50 ° C., 0.02 mol / L of palladium sulfate, 0.04 mol / L of ethylenediamine as a complexing agent, 0.06 mol / L of sodium formate as a reducing agent, and pH 10.0 containing a crystal modifier. The electroless plating solution was gradually added to perform electroless palladium plating. When the thickness of the palladium layer reached 0.03 ⁇ m, the electroless palladium plating was finished. Next, by washing and vacuum drying, conductive particles having a palladium layer formed on the surface of the nickel layer were obtained.
  • Example 2 Electroless nickel plating step Divinylbenzene resin particles having an average particle diameter of 4 ⁇ m were treated with a 10 wt% solution of an ion adsorbent for 5 minutes, and then treated with a 0.01 wt% palladium sulfate aqueous solution for 5 minutes. Thereafter, dimethylamine borane was added for reduction treatment, filtration, and washing to obtain resin particles to which palladium was attached.
  • a 1% by weight sodium succinate solution in which sodium succinate was dissolved in 500 mL of ion-exchanged water was prepared.
  • 10 g of resin particles with palladium attached were added and mixed to prepare a slurry.
  • the pH of the slurry was adjusted to 9.0.
  • an initial nickel solution containing 10% by weight of nickel sulfate, 10% by weight of sodium hypophosphite, 4% by weight of sodium hydroxide and 20% by weight of sodium succinate was prepared.
  • the slurry adjusted to pH 9.0 was heated to 80 ° C., and then the nickel solution was continuously added dropwise to the slurry and stirred for 20 minutes to advance the plating reaction. After confirming that hydrogen was no longer generated, the plating reaction was completed.
  • a late nickel solution containing 20% by weight of nickel sulfate, 20% by weight of sodium hypophosphite and 15% by weight of sodium hydroxide was prepared.
  • the late nickel solution was continuously added dropwise to the solution that had finished the plating reaction with the previous nickel solution, and the plating reaction was allowed to proceed by stirring for 1 hour. In this way, a nickel layer was formed on the surface of the resin particles to obtain nickel plated particles.
  • the nickel layer had a thickness of 0.1 ⁇ m.
  • Example 3 Electroless nickel plating step Divinylbenzene resin particles having an average particle diameter of 4 ⁇ m were treated with a 10 wt% solution of an ion adsorbent for 5 minutes, and then treated with a 0.01 wt% palladium sulfate aqueous solution for 5 minutes. Thereafter, dimethylamine borane was added for reduction treatment, filtration, and washing to obtain resin particles to which palladium was attached.
  • a 1% by weight sodium succinate solution in which sodium succinate was dissolved in 500 mL of ion-exchanged water was prepared.
  • 10 g of resin particles with palladium attached were added and mixed to prepare a slurry.
  • the pH of the slurry was adjusted to 4.5.
  • As a nickel plating solution an initial nickel solution containing 10% by weight of nickel sulfate, 10% by weight of sodium hypophosphite, 4% by weight of sodium hydroxide and 20% by weight of sodium succinate was prepared.
  • the slurry adjusted to pH 4.5 was heated to 80 ° C., and then the nickel solution was continuously added dropwise to the slurry and stirred for 20 minutes to advance the plating reaction. After confirming that hydrogen was no longer generated, the plating reaction was completed.
  • a late nickel solution containing 20% by weight of nickel sulfate, 30% by weight of sodium hypophosphite and 5% by weight of sodium hydroxide was prepared.
  • the late nickel solution was continuously added dropwise to the solution that had finished the plating reaction with the previous nickel solution, and the plating reaction was allowed to proceed by stirring for 1 hour. In this way, a nickel layer was formed on the surface of the resin particles to obtain nickel plated particles.
  • the nickel layer had a thickness of 0.1 ⁇ m.
  • Example 4 Electroless nickel plating step (step of forming protrusions on the surface of the nickel layer) 1-1)
  • Palladium adhesion step 10 g of divinylbenzene resin particles having an average particle diameter of 4 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
  • Electroless palladium plating step Conductive particles having a palladium layer formed on the surface of the nickel layer are obtained by performing the same electroless palladium plating step as in Example 1 using 10 g of the obtained nickel plating particles. Obtained. The obtained conductive particles had protrusions on the surface.
  • the conductive particles were obtained in the same manner as in Example 4 except that the change was made to). The obtained conductive particles had protrusions on the surface.
  • Example 6 (1) Production of insulating resin particles In a 1000 mL separable flask equipped with a four-neck separable cover, a stirring blade, a three-way cock, a condenser tube and a temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, freeze drying was performed to obtain insulating resin particles having an ammonium group on the surface, an average particle diameter of 220 nm, and a CV value of 10%.
  • the insulating resin particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating resin particles.
  • Example 5 10 g of the conductive particles obtained in Example 5 were dispersed in 500 mL of ion exchange water, 4 g of an aqueous dispersion of insulating resin particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 ⁇ m mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating resin particles attached thereto.
  • the conductive particles were obtained in the same manner as in Example 1 except that the above was changed.
  • Example 8 Except having changed the electroconductive particle obtained in Example 5 into the electroconductive particle obtained in Example 1, it carried out similarly to Example 6, and obtained the electroconductive particle to which the insulating resin particle adhered.
  • Example 9 Except having changed the electroconductive particle obtained in Example 5 into the electroconductive particle obtained in Example 4, it carried out similarly to Example 6, and obtained the electroconductive particle to which the insulating resin particle adhered.
  • Example 10 Except having changed the electroconductive particle obtained in Example 5 into the electroconductive particle obtained in Example 7, it carried out similarly to Example 6, and obtained the electroconductive particle to which the insulating resin particle adhered.
  • Example 11 Electroless nickel plating step In the same manner as in the electroless nickel plating step of Example 1, nickel plated particles having a nickel layer formed on the surface of the resin particles were obtained.
  • Electroless palladium plating step Except for changing to an electroless plating solution having a pH of 9.0 containing 0.035 mol / L of ethylenediamine as a complexing agent, 0.05 mol / L of sodium formate as a reducing agent and a crystal modifier, In the same manner as in Example 1, conductive particles having a palladium layer formed on the surface of the nickel layer were obtained.
  • Example 2 In the electroless nickel plating step, the pH was adjusted to 7.5 when adjusting the pH, and nickel sulfate 10 wt%, sodium hypophosphite 10 wt%, sodium hydroxide 4 wt%, and sodium succinate 20 Example 1 except that the nickel solution containing 10% by weight was changed to a nickel solution containing 10% by weight nickel sulfate, 6% by weight sodium hypophosphite, 4% by weight sodium hydroxide and 20% by weight sodium succinate. In the same manner as in Example 1, conductive particles having a nickel layer formed on the surface of the resin particles and a palladium layer formed on the surface of the nickel layer were obtained.
  • Example 3 In the electroless nickel plating step, the pH of the slurry was adjusted to 4.5, and 10% by weight of nickel sulfate, 10% by weight of sodium hypophosphite, 4% by weight of sodium hydroxide and 20% by weight of sodium succinate were included.
  • Example 1 was the same as Example 1 except that the nickel solution was changed to a nickel solution containing 10% by weight nickel sulfate, 30% by weight sodium hypophosphite, 4% by weight sodium hydroxide and 20% by weight sodium succinate.
  • conductive particles having a nickel layer formed on the surface of the resin particles and a palladium layer formed on the surface of the nickel layer were obtained.
  • Electroless palladium plating step Except for changing to an electroless plating solution having a pH of 8.5 containing ethylenediamine 0.030 mol / L as a complexing agent, sodium formate 0.04 mol / L as a reducing agent and a crystal modifier, In the same manner as in Example 1, conductive particles having a palladium layer formed on the surface of the nickel layer were obtained.
  • the anisotropic conductive paste After applying the anisotropic conductive paste on the upper surface of the substrate so that the conductive particles are in contact with the copper electrode, the other substrate is laminated so that the copper electrode is in contact with the conductive particles, and is bonded to obtain a laminate. It was. Then, the anisotropic conductive paste was hardened by heating a laminated body at 180 degreeC for 1 minute, and the connection structure was obtained.
  • connection resistance between the opposing electrodes of the obtained connection structure was measured by the four-terminal method, and the obtained measurement value was used as the initial connection resistance.
  • connection resistance between the electrodes of the connection structure after being allowed to stand was measured by the four-terminal method, and the obtained measured value was used as the connection resistance after the high temperature and high humidity test.
  • a prepared substrate was prepared.
  • 10 parts by weight of the conductive particles obtained in Examples and Comparative Examples 85 parts by weight of an epoxy resin (“Stractbond XN-5A” manufactured by Mitsui Chemicals) as a binder resin, and 5 parts by weight of an imidazole type curing agent
  • An anisotropic conductive paste containing was prepared.
  • An anisotropic conductive paste was applied to the upper surfaces of the copper patterns 31 and 32 of the substrate, and then an alkali-free glass plate was laminated and pressed, and the conductive particles were brought into contact with the copper patterns 31 and 32.
  • the anisotropic conductive paste was hardened by heating at 180 degreeC for 1 minute, and the connection structure was obtained.
  • the insulation resistance between the adjacent electrodes of the obtained connection structure was measured by a four-terminal method, and the obtained measurement value was used as the initial insulation resistance.
  • connection structure was allowed to stand for 1000 hours under conditions of 85 ° C. and 85% humidity while applying a bias voltage of 50 V between the electrodes.
  • the insulation resistance between the adjacent electrodes of the connection structure after being allowed to stand was measured by the four-terminal method, and the obtained measurement value was taken as the insulation resistance after the high temperature and high humidity test.
  • SYMBOLS 1 Conductive particle 2 ... Base particle 2a ... Surface 3 ... Nickel layer 3a ... Surface 4 ... Palladium layer 4a ... Surface 11 ... Connection structure 12 ... Circuit board 12a ... Electrode 13 ... Connection part 14 ... Semiconductor chip 14a ... Electrode DESCRIPTION OF SYMBOLS 21 ... Conductive particle 21a ... Surface 22 ... Nickel layer 22a ... Surface 23 ... Palladium layer 23a ... Surface 24 ... Core substance 25 ... Projection 26 ... Insulating resin 31, 32 ... Copper electrode copper pattern

Abstract

Disclosed is an electroconductive particle, an anisotropic electroconductive material using same, and a connection structure; where when the connection structure is formed connecting across a gap between electrodes, connection resistance between the electrodes does not increase even when the connecting structure is exposed to high heat and high humidity. The electroconductive particle (1) is comprised of a substrate particle (2), a nickel layer (3) formed on a surface (2a) of the substrate particle (2), and a palladium layer (4) formed on a surface (3a) of the nickel layer (3). In the electroconductive particle (1), the nickel layer has a phosphorus content in the region of 5-15%, and the palladium layer has a palladium content of 96% or above.

Description

導電性粒子、異方性導電材料及び接続構造体Conductive particles, anisotropic conductive materials, and connection structures
　本発明は、電極間の接続に使用できる導電性粒子に関し、より詳細には、電極間の接続に用いられた場合に、電極間の接続信頼性を高めることができる導電性粒子、該導電性粒子を用いた異方性導電材料及び接続構造体に関する。 The present invention relates to conductive particles that can be used for connection between electrodes, and more specifically, conductive particles that can improve connection reliability between electrodes when used for connection between electrodes, and the conductive property. The present invention relates to an anisotropic conductive material using particles and a connection structure.
　異方性導電ペースト、異方性導電インク、異方性導電粘接着剤、異方性導電フィルム、又は異方性導電シート等の異方性導電材料が広く知られている。これらの異方性導電材料では、ペースト、インク又は樹脂中に導電性粒子が分散されている。 Anisotropic conductive materials such as anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, anisotropic conductive film, or anisotropic conductive sheet are widely known. In these anisotropic conductive materials, conductive particles are dispersed in paste, ink, or resin.
　異方性導電材料は、ＩＣチップとフレキシブルプリント回路基板との接続、及びＩＣチップとＩＴＯ電極を有する回路基板との接続等に使用されている。例えば、ＩＣチップの電極と回路基板の電極との間に異方性導電材料を配置した後、加熱及び加圧することにより、これらの電極同士を接続できる。 The anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, connection between an IC chip and a circuit board having an ITO electrode, and the like. For example, after an anisotropic conductive material is arranged between the electrode of the IC chip and the electrode of the circuit board, these electrodes can be connected by heating and pressurizing.
　上記異方性導電材料に用いられる導電性粒子の一例として、下記の特許文献１には、基材粒子と、該基材粒子の表面に形成されたニッケル層と、該ニッケル層の表面に形成されたパラジウム層とを備える導電性粒子が開示されている。 As an example of the conductive particles used for the anisotropic conductive material, the following Patent Document 1 discloses base material particles, a nickel layer formed on the surface of the base material particle, and formed on the surface of the nickel layer. Disclosed is a conductive particle comprising a modified palladium layer.
特開２００７－３０５５８３号公報JP 2007-305583 A
　特許文献１に記載の導電性粒子を電極間の接続に用いて、接続構造体を形成した場合、該接続構造体が高温高湿下に晒されたときに、電極間の接続抵抗が高くなることがある。 When the connection structure is formed using the conductive particles described in Patent Document 1 for connection between the electrodes, the connection resistance between the electrodes becomes high when the connection structure is exposed to high temperature and high humidity. Sometimes.
　本発明の目的は、電極間を接続して接続構造体を形成した場合、該接続構造体が高温高湿下に晒されても、電極間の接続抵抗が高くなり難い導電性粒子、並びに該導電性粒子を用いた異方性導電材料及び接続構造体を提供することである。 An object of the present invention is to form a connection structure by connecting electrodes, and even when the connection structure is exposed to high temperature and high humidity, the conductive particles that do not easily increase the connection resistance between the electrodes, and the An anisotropic conductive material using a conductive particle and a connection structure are provided.
　本発明の広い局面によれば、基材粒子と、該基材粒子の表面に形成されたニッケル層と、該ニッケル層の表面に形成されたパラジウム層とを備えており、上記ニッケル層のリンの含有率が５～１５重量％の範囲内であり、かつ上記パラジウム層のパラジウムの含有率が９６重量％以上である、導電性粒子が提供される。 According to a wide aspect of the present invention, there are provided base particles, a nickel layer formed on the surface of the base particles, and a palladium layer formed on the surface of the nickel layer. There is provided conductive particles having a palladium content of 5 to 15% by weight and a palladium content of the palladium layer of 96% by weight or more.
　本発明のある特定の局面では、導電性粒子は表面に突起を有する。本発明の他の特定の局面では、導電性粒子は、パラジウム層の外側の表面に突起を有する。 In one specific aspect of the present invention, the conductive particles have protrusions on the surface. In another specific aspect of the present invention, the conductive particles have protrusions on the outer surface of the palladium layer.
　本発明に係る導電性粒子の他の特定の局面では、上記パラジウム層の表面に付着された絶縁性樹脂がさらに備えられる。 In another specific aspect of the conductive particle according to the present invention, an insulating resin attached to the surface of the palladium layer is further provided.
　本発明に係る導電性粒子の他の特定の局面では、上記絶縁性樹脂は絶縁樹脂粒子である。 In another specific aspect of the conductive particle according to the present invention, the insulating resin is an insulating resin particle.
　本発明に係る異方性導電材料は、本発明に従って構成された導電性粒子と、バインダー樹脂とを含む。 The anisotropic conductive material according to the present invention includes conductive particles configured according to the present invention and a binder resin.
　本発明に係る接続構造体は、第１の接続対象部材と、第２の接続対象部材と、該第１，第２の接続対象部材を電気的に接続している接続部とを備えており、上記接続部が本発明の導電性粒子又は該導電性粒子とバインダー樹脂とを含む異方性導電材料により形成されている。 The connection structure according to the present invention includes a first connection target member, a second connection target member, and a connection part that electrically connects the first and second connection target members. The connecting portion is made of the conductive particles of the present invention or an anisotropic conductive material containing the conductive particles and a binder resin.
　本発明に係る導電性粒子は、基材粒子の表面にニッケル層とパラジウム層とがこの順で形成されており、ニッケル層のリンの含有率が５～１５重量％の範囲内であり、かつパラジウム層のパラジウムの含有率が９６重量％以上であるため、導電性粒子を電極間の接続に用いた接続構造体が高温高湿下に晒された場合に、接続抵抗が高くなるのを抑制できる。従って、接続構造体の接続信頼性を高めることができる。 In the conductive particles according to the present invention, a nickel layer and a palladium layer are formed in this order on the surface of the base particle, the phosphorus content of the nickel layer is in the range of 5 to 15% by weight, and Since the palladium content in the palladium layer is 96% by weight or more, it prevents the connection resistance from increasing when a connection structure using conductive particles for connection between electrodes is exposed to high temperature and high humidity. it can. Therefore, the connection reliability of the connection structure can be improved.
図１は、本発明の一実施形態に係る導電性粒子を示す断面図である。FIG. 1 is a cross-sectional view showing conductive particles according to an embodiment of the present invention. 図２は、本発明の他の実施形態に係る導電性粒子を示す断面図である。FIG. 2 is a cross-sectional view showing conductive particles according to another embodiment of the present invention. 図３は、本発明の一実施形態に係る導電性粒子を用いた接続構造体を模式的に示す正面断面図である。FIG. 3 is a front sectional view schematically showing a connection structure using conductive particles according to an embodiment of the present invention. 図４は、実施例及び比較例の絶縁抵抗の評価に際に用いた基板上のくし歯電極銅パターンの形状を説明するための平面図である。FIG. 4 is a plan view for explaining the shape of the comb-shaped electrode copper pattern on the substrate used in the evaluation of the insulation resistance of the example and the comparative example.
　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
　図１は、本発明の一実施形態に係る導電性粒子を示す断面図である。 FIG. 1 is a cross-sectional view showing conductive particles according to an embodiment of the present invention.
　図１に示すように、導電性粒子１は、基材粒子２と、該基材粒子２の表面２ａに形成されたニッケル層３と、該ニッケル層３の表面３ａに形成されたパラジウム層４とを備える。導電性粒子１は、パラジウム層４の表面４ａに付着された絶縁性樹脂をさらに備えていてもよい。 As shown in FIG. 1, the conductive particles 1 include a base particle 2, a nickel layer 3 formed on the surface 2 a of the base particle 2, and a palladium layer 4 formed on the surface 3 a of the nickel layer 3. With. The conductive particles 1 may further include an insulating resin attached to the surface 4 a of the palladium layer 4.
　図２は、本発明の他の実施形態に係る導電性粒子を示す断面図である。 FIG. 2 is a cross-sectional view showing conductive particles according to another embodiment of the present invention.
　図２に示すように、導電性粒子２１は、基材粒子２と、該基材粒子２の表面２ａに形成されたニッケル層２２と、該ニッケル層２２の表面２２ａに形成されたパラジウム層２３とを備える。ニッケル層２２とパラジウム層２３とは金属層である。導電性粒子２１は、基材粒子２の表面２ａに複数の芯物質２４を備える。金属層であるニッケル層２２及びパラジウム層２３は、芯物質２４を被覆している。芯物質２４を金属層が被覆していることにより、導電性粒子２１は表面２１ａに複数の突起２５を有する。導電性粒子２１は、パラジウム層２３の外側の表面２３ａに複数の突起２５を有する。突起２５は、金属層の外側のパラジウム層２３の表面２３ａに形成されている。芯物質２４によりパラジウム層２３の表面２３ａが隆起されており、突起２５が形成されている。 As shown in FIG. 2, the conductive particles 21 include base material particles 2, a nickel layer 22 formed on the surface 2 a of the base material particle 2, and a palladium layer 23 formed on the surface 22 a of the nickel layer 22. With. The nickel layer 22 and the palladium layer 23 are metal layers. The conductive particle 21 includes a plurality of core substances 24 on the surface 2 a of the base particle 2. The nickel layer 22 and the palladium layer 23 that are metal layers cover the core substance 24. By covering the core substance 24 with the metal layer, the conductive particles 21 have a plurality of protrusions 25 on the surface 21a. The conductive particle 21 has a plurality of protrusions 25 on the outer surface 23 a of the palladium layer 23. The protrusion 25 is formed on the surface 23a of the palladium layer 23 outside the metal layer. A surface 23 a of the palladium layer 23 is raised by the core material 24, and a protrusion 25 is formed.
　導電性粒子２１は、パラジウム層２３の表面２３ａに付着された絶縁性樹脂２６を備える。パラジウム層２３の表面は、絶縁性樹脂２６により被覆されている。本実施形態では、絶縁性樹脂２６は絶縁樹脂粒子である。このように、導電性粒子は、パラジウム層２３の表面２３ａを被覆している絶縁性樹脂２６を備えていてもよい。ただし、絶縁性樹脂２６は、必ずしも備えられていなくてもよい。 The conductive particles 21 include an insulating resin 26 attached to the surface 23 a of the palladium layer 23. The surface of the palladium layer 23 is covered with an insulating resin 26. In the present embodiment, the insulating resin 26 is insulating resin particles. Thus, the conductive particles may include an insulating resin 26 that covers the surface 23a of the palladium layer 23. However, the insulating resin 26 is not necessarily provided.
　基材粒子２としては、樹脂粒子、無機粒子、有機無機ハイブリッド粒子又は金属粒子等が挙げられる。 Examples of the base particle 2 include resin particles, inorganic particles, organic-inorganic hybrid particles, and metal particles.
　上記樹脂粒子を形成するための樹脂としては、例えば、ジビニルベンゼン樹脂、スチレン樹脂、アクリル樹脂、尿素樹脂、イミド樹脂、フェノール樹脂、ポリエステル樹脂又は塩化ビニル樹脂等が挙げられる。上記無機粒子を形成するための無機物としては、シリカ又はカーボンブラック等が挙げられる。上記有機無機ハイブリッド粒子としては、例えば、架橋したアルコキシシリルポリマーとアクリル樹脂とにより形成された有機無機ハイブリッド粒子等が挙げられる。上記金属粒子を形成するための金属としては、銀、銅、ニッケル、ケイ素、金又はチタン等が挙げられる。 Examples of the resin for forming the resin particles include divinylbenzene resin, styrene resin, acrylic resin, urea resin, imide resin, phenol resin, polyester resin, and vinyl chloride resin. Examples of the inorganic material for forming the inorganic particles include silica or carbon black. Examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin. Examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium.
　基材粒子２の平均粒子径は、１～１００μｍの範囲内であることが好ましい。基材粒子の平均粒子径が１μｍよりも小さいと、電極間の接続信頼性が低下することがある。基材粒子の平均粒子径が１００μｍよりも大きいと、電極間の間隔が大きくなりすぎることがある。 The average particle diameter of the base particle 2 is preferably in the range of 1 to 100 μm. When the average particle diameter of the substrate particles is smaller than 1 μm, the connection reliability between the electrodes may be lowered. When the average particle diameter of the substrate particles is larger than 100 μm, the distance between the electrodes may be too large.
　基材粒子２の表面２ａに形成されるニッケル層３，２２のリンの含有率は５～１５重量％の範囲内である。リンの含有率が５重量％未満であると、導電性粒子を電極間の接続に用いた接続構造体が高温高湿下に晒された場合に、接続抵抗が高くなる。リンの含有率が１５重量％を超えると、導電性粒子を電極間の接続に用いた接続構造体の初期接続抵抗が高くなる。また、ニッケル層３，２２のリンの含有率が５～１５重量％であることにより、微細なニッケル結晶を得やすくなり、かつパラジウムめっきのエピタキシャル成長により微細なパラウム結晶を得やすくなる。このため、接続構造体の高温高湿下での接続信頼性を高めることができる。上記ニッケル層３，２２のリンの含有率は１０～１５重量％の範囲内にあることが好ましい。上記ニッケル層３，２２のリンの含有率が１０～１５重量％の範囲内であることにより、接続構造体の高温高湿下での接続信頼性をより一層高めることができる。 The content of phosphorus in the nickel layers 3 and 22 formed on the surface 2a of the base particle 2 is in the range of 5 to 15% by weight. When the phosphorus content is less than 5% by weight, the connection resistance increases when the connection structure using the conductive particles for connection between the electrodes is exposed to high temperature and high humidity. When the phosphorus content exceeds 15% by weight, the initial connection resistance of the connection structure using the conductive particles for connection between the electrodes becomes high. Further, when the content of phosphorus in the nickel layers 3 and 22 is 5 to 15% by weight, it becomes easy to obtain fine nickel crystals, and it becomes easy to obtain fine palladium crystals by epitaxial growth of palladium plating. For this reason, the connection reliability of the connection structure under high temperature and high humidity can be improved. The phosphorus content in the nickel layers 3 and 22 is preferably in the range of 10 to 15% by weight. When the content of phosphorus in the nickel layers 3 and 22 is in the range of 10 to 15% by weight, the connection reliability of the connection structure under high temperature and high humidity can be further improved.
　ニッケル層３，２２のリンの含有率を上記範囲内にする方法としては、例えば、無電解ニッケルめっきによりニッケル層を形成する際に、ニッケルめっき液のｐＨを制御する方法、又は無電解ニッケルめっきによりニッケル層を形成する際に、リン含有還元剤の濃度を制御する方法等が挙げられる。 As a method of bringing the phosphorus content of the nickel layers 3 and 22 into the above range, for example, a method of controlling the pH of a nickel plating solution when forming a nickel layer by electroless nickel plating, or electroless nickel plating For example, a method of controlling the concentration of the phosphorus-containing reducing agent when forming the nickel layer by the method described above.
　なお、上記ニッケル層のリンの含有率の測定方法は特に限定されないが、例えば、集束イオンビームを用いて、得られた導電性粒子の薄膜切片を作製し、透過型電子顕微鏡ＦＥ－ＴＥＭ（日本電子社製「ＪＥＭ－２０１０ＦＥＦ」）を用いて、エネルギー分散型Ｘ線分析装置（ＥＤＳ）により、ニッケル層のリンの含有率を測定する方法が挙げられる。 The method for measuring the phosphorus content of the nickel layer is not particularly limited. For example, a thin film section of the obtained conductive particles is prepared using a focused ion beam, and a transmission electron microscope FE-TEM (Japan) A method of measuring the content of phosphorus in the nickel layer with an energy dispersive X-ray analyzer (EDS) using “JEM-2010FEF” manufactured by Denshi Co., Ltd.
　ニッケル層３，２２の表面３ａ，２２ａに形成されるパラジウム層４，２３のパラジウムの含有率は９６重量％以上である。パラジウムの含有率が９６重量％未満であると、導電性粒子を電極間の接続に用いた接続構造体が高温高湿下に晒された場合に、接続抵抗が高くなる。パラジウムの含有率は９８重量％以上であることが好ましい。 The palladium content of the palladium layers 4 and 23 formed on the surfaces 3a and 22a of the nickel layers 3 and 22 is 96% by weight or more. When the palladium content is less than 96% by weight, the connection resistance increases when the connection structure using the conductive particles for connection between the electrodes is exposed to high temperature and high humidity. The palladium content is preferably 98% by weight or more.
　パラジウム層４，２３のパラジウムの含有率を９６重量％以上にする方法としては、例えば、無電解パラジウムめっきによりパラジウム層を形成する際に、パラジウムめっき液のｐＨを制御する方法、又は無電解パラジウムめっきによりパラジウム層を形成する際に、還元剤の濃度を制御する方法等が挙げられる。 Examples of a method for making the palladium content of the palladium layers 4 and 23 96% by weight or more include a method of controlling the pH of the palladium plating solution when forming a palladium layer by electroless palladium plating, or electroless palladium. For example, a method of controlling the concentration of the reducing agent when forming the palladium layer by plating may be used.
　なお、上記パラジウム層のパラジウムの含有率の測定方法は特に限定されないが、例えば、集束イオンビームを用いて、得られた導電性粒子の薄膜切片を作製し、透過型電子顕微鏡ＦＥ－ＴＥＭ（日本電子社製「ＪＥＭ－２０１０ＦＥＦ」）を用いて、エネルギー分散型Ｘ線分析装置（ＥＤＳ）により、パラジウム層のパラジウムの含有率を測定する方法が挙げられる。 The method for measuring the palladium content in the palladium layer is not particularly limited. For example, a thin film slice of the obtained conductive particles is prepared using a focused ion beam, and a transmission electron microscope FE-TEM (Japan) A method of measuring the palladium content of the palladium layer with an energy dispersive X-ray analyzer (EDS) using “JEM-2010FEF” manufactured by Denshi Co., Ltd.
　ニッケル層３，２２とパラジウム層４，２３との金属層の合計厚みは、５～５００ｎｍの範囲内であることが好ましく、１０～４００ｎｍの範囲内であることがより好ましい。金属層の厚みが５ｎｍ未満であると、導電性粒子の導電性が不足することがある。金属層の厚みが５００ｎｍを超えると、基材粒子と金属層との熱膨張率の差が大きくなり、基材粒子から金属層が剥離しやすくなることがある。 The total thickness of the metal layers of the nickel layers 3 and 22 and the palladium layers 4 and 23 is preferably in the range of 5 to 500 nm, and more preferably in the range of 10 to 400 nm. When the thickness of the metal layer is less than 5 nm, the conductivity of the conductive particles may be insufficient. When the thickness of the metal layer exceeds 500 nm, the difference in coefficient of thermal expansion between the base particle and the metal layer becomes large, and the metal layer may easily peel from the base particle.
　基材粒子２の表面２ａにニッケル層３，２２を形成する方法としては、無電解めっきによりニッケル層を形成する方法又は電気めっきによりニッケル層を形成する方法等が挙げられる。 Examples of the method of forming the nickel layers 3 and 22 on the surface 2a of the base particle 2 include a method of forming a nickel layer by electroless plating or a method of forming a nickel layer by electroplating.
　また、ニッケル層３，２２の表面３ａ，２２ａにパラジウム層４，２３を形成する方法としては、無電解めっきによりパラジウム層を形成する方法又は電気めっきによりパラジウム層を形成する方法等が挙げられる。 Also, examples of the method of forming the palladium layers 4 and 23 on the surfaces 3a and 22a of the nickel layers 3 and 22 include a method of forming a palladium layer by electroless plating or a method of forming a palladium layer by electroplating.
　導電性粒子２１のように、導電性粒子は表面に突起を有することが好ましい。導電性粒子は、金属層の表面に突起を有することが好ましく、更にパラジウム層４，２３の表面４ａ，２３ａに突起を有することが好ましい。導電性粒子は表面に複数の突起を有することが好ましい。導電性粒子は、金属層の表面に複数の突起を有することが好ましく、更にパラジウム層４，２３の表面４ａ，２３ａに複数の突起を有することが好ましい。これらの場合には、導電性粒子と電極との間の樹脂を効果的に排除できるので、導電性粒子を電極間の接続に用いた接続構造体の接続信頼性を高めることができる。 Like the conductive particles 21, the conductive particles preferably have protrusions on the surface. The conductive particles preferably have protrusions on the surface of the metal layer, and further preferably have protrusions on the surfaces 4a and 23a of the palladium layers 4 and 23. The conductive particles preferably have a plurality of protrusions on the surface. The conductive particles preferably have a plurality of protrusions on the surface of the metal layer, and more preferably have a plurality of protrusions on the surfaces 4 a and 23 a of the palladium layers 4 and 23. In these cases, since the resin between the conductive particles and the electrodes can be effectively eliminated, the connection reliability of the connection structure using the conductive particles for the connection between the electrodes can be improved.
　導電性粒子の表面に突起を形成する方法としては、基材粒子の表面に芯物質を付着させた後、無電解めっきにより金属層を形成する方法、又は基材粒子の表面に無電解めっきにより金属層を形成した後、芯物質を付着させ、更に無電解めっきにより金属層を形成する方法等が挙げられる。 As a method of forming protrusions on the surface of the conductive particles, a method of forming a metal layer by electroless plating after attaching a core substance to the surface of the base particles, or by electroless plating on the surface of the base particles Examples include a method of forming a metal layer by electroless plating after a core layer is adhered after forming the metal layer.
　基材粒子の表面に芯物質を付着させる方法としては、例えば、基材粒子の分散液中に、芯物質となる導電性物質を添加し、基材粒子の表面に芯物質を、例えば、ファンデルワールス力により集積させ、付着させる方法、又は基材粒子を入れた容器に、芯物質となる導電性物質を添加し、容器の回転等による機械的な作用により基材粒子の表面に芯物質を付着させる方法等が挙げられる。なかでも、付着させる芯物質の量を制御しやすいため、分散液中の基材粒子の表面に芯物質を集積させ付着させる方法が好ましい。 As a method of attaching the core substance to the surface of the base particle, for example, a conductive substance that becomes 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, a fan. A method of accumulating and adhering by Delwars force, or adding a conductive substance as a core substance to a container containing base particles, and a core substance on the surface of the base particles by mechanical action such as rotation of the container And the like. Among them, a method of accumulating and adhering the core substance on the surface of the base particle in the dispersion is preferable because the amount of the core substance to be attached is easy to control.
　上記芯物質を構成する導電性物質としては、例えば、金属、金属の酸化物、黒鉛等の導電性非金属又は導電性ポリマー等が挙げられる。導電性ポリマーとしては、ポリアセチレン等が挙げられる。なかでも、導電性を高めることができるので、金属が好ましい。 Examples of the conductive substance constituting the core substance include metals, metal oxides, conductive nonmetals such as graphite, and conductive polymers. Examples of the conductive polymer include polyacetylene. Among them, metal is preferable because conductivity can be increased.
　上記金属としては、例えば、金、銀、銅、白金、亜鉛、鉄、鉛、錫、アルミニウム、コバルト、インジウム、ニッケル、クロム、チタン、アンチモン、ビスマス、ゲルマニウム及びカドミウム等の金属、並びに錫－鉛合金、錫－銅合金、錫－銀合金及び錫－鉛－銀合金等の２種類以上の金属で構成される合金等が挙げられる。なかでも、ニッケル、銅、銀又は金等が好ましい。上記芯物質を構成する金属は、上記金属層を構成する金属と同じであってもよく、異なっていてもよい。 Examples of the metal include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead. Examples thereof include alloys composed of two or more metals such as alloys, tin-copper alloys, tin-silver alloys, and tin-lead-silver alloys. Of these, nickel, copper, silver or gold is preferable. The metal constituting the core material may be the same as or different from the metal constituting the metal layer.
　上記芯物質の形状は特に限定されない。芯物質の形状は塊状であることが好ましい。芯物質としては、例えば、粒子状の塊、複数の微小粒子が凝集した凝集塊、不定形の塊等が挙げられる。 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 obtained by aggregating a plurality of fine particles, and an irregular lump.
　導電性粒子２１のように、本発明に係る導電性粒子は、上記パラジウム層の表面に付着された絶縁性樹脂をさらに備えることが好ましい。この場合には、導電性粒子を電極間の接続に用いると、隣接する電極間の短絡を防止することができる。具体的には、複数の導電性粒子が接触したときに、複数の電極間に絶縁性樹脂が存在するので、上下の電極間ではなく横方向に隣り合う電極間の短絡を防止することができる。なお、電極間の接続の際に、２つの電極で導電性粒子を加圧することにより、導電性粒子の金属層と電極との間の絶縁性樹脂を容易に排除できる。導電性粒子がパラジウム層の表面に突起を有する場合には、導電性粒子の金属層と電極との間の絶縁性樹脂をより一層容易に排除できる。 Like the conductive particles 21, the conductive particles according to the present invention preferably further include an insulating resin attached to the surface of the palladium layer. In this case, when the conductive particles are used for connection between the electrodes, a short circuit between adjacent electrodes can be prevented. Specifically, when a plurality of conductive particles are in contact with each other, an insulating resin is present between the plurality of electrodes, so that it is possible to prevent a short circuit between electrodes adjacent in the lateral direction instead of between the upper and lower electrodes. . In addition, the insulating resin between the metal layer of an electroconductive particle and an electrode can be easily excluded by pressurizing electroconductive particle with two electrodes in the case of the connection between electrodes. When the conductive particles have protrusions on the surface of the palladium layer, the insulating resin between the metal layer of the conductive particles and the electrode can be more easily removed.
　上記絶縁性樹脂の具体例としては、ポリオレフィン類、（メタ）アクリレート重合体、（メタ）アクリレート共重合体、ブロックポリマー、熱可塑性樹脂、熱可塑性樹脂の架橋物、熱硬化性樹脂又は水溶性樹脂等が挙げられる。 Specific examples of the insulating resin include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked thermoplastic resins, thermosetting resins or water-soluble resins. Etc.
　上記ポリオレフィン類としては、ポリエチレン、エチレン－酢酸ビニル共重合体又はエチレン－アクリル酸エステル共重合体等が挙げられる。上記（メタ）アクリレート重合体としては、ポリメチル（メタ）アクリレート、ポリエチル（メタ）アクリレート又はポリブチル（メタ）アクリレート等が挙げられる。上記ブロックポリマーとしては、ポリスチレン、スチレン－アクリル酸エステル共重合体、ＳＢ型スチレン－ブタジエンブロック共重合体、又はＳＢＳ型スチレン－ブタジエンブロック共重合体、及びこれらの水添化合物等が挙げられる。上記熱可塑性樹脂としては、ビニル重合体又はビニル共重合体等が挙げられる。上記熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂又はメラミン樹脂等が挙げられる。上記水溶性樹脂としては、ポリビニルアルコール、ポリアクリル酸、ポリアクリルアミド、ポリビニルピロリドン、ポリエチレンオキシド又はメチルセルロース等が挙げられる。なかでも、水溶性樹脂が好ましく、ポリビニルアルコールがより好ましい。 Examples of the polyolefins include polyethylene, ethylene-vinyl acetate copolymer or ethylene-acrylic 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 compounds thereof. Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers. Examples of the thermosetting resin include an epoxy resin, a phenol resin, and a melamine resin. Examples of the water-soluble resin 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.
　上記パラジウム層の表面に絶縁性樹脂を付着させる方法としては、化学的方法、又は物理的もしくは機械的方法等が挙げられる。上記化学的方法としては、例えば、界面重合法、粒子存在下での懸濁重合法又は乳化重合法等が挙げられる。上記物理的もしくは機械的方法としては、スプレードライ、ハイブリタイゼーション、静電付着法、噴霧法、ディッピング又は真空蒸着による方法等が挙げられる。 As a method for attaching an insulating resin to the surface of the palladium layer, a chemical method, a physical or mechanical method, and the like can be given. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, or an emulsion polymerization method. Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spraying, dipping, or vacuum deposition.
　上記絶縁性樹脂は、絶縁樹脂粒子であることが好ましい。この場合には、導電性粒子を電極間の接続に用いると、隣接する電極間の短絡を防止することができるだけでなく、対向する電極間の接続抵抗を低減することができる。 The insulating resin is preferably insulating resin particles. In this case, when the conductive particles are used for connection between the electrodes, not only can a short circuit between adjacent electrodes be prevented, but also the connection resistance between the opposing electrodes can be reduced.
　上記パラジウム層の表面に絶縁樹脂粒子を付着させる方法としては、化学的方法、又は物理的もしくは機械的方法等が挙げられる。上記化学的方法としては、例えば、パラジウム層の表面に、化学結合を介して絶縁樹脂粒子を付着させる方法等が挙げられる。上記物理的もしくは機械的方法としては、ハイブリタイゼーション又は静電付着法による方法等が挙げられる。なかでも、絶縁樹脂粒子が剥離しにくいことから、パラジウム層の表面に、化学結合を介して絶縁樹脂粒子を付着させる方法が好ましい。 As a method for attaching the insulating resin particles to the surface of the palladium layer, a chemical method, a physical or mechanical method, and the like can be given. Examples of the chemical method include a method of attaching insulating resin particles to the surface of the palladium layer through a chemical bond. Examples of the physical or mechanical method include a method using hybridization or an electrostatic adhesion method. In particular, since the insulating resin particles are difficult to peel off, a method of attaching the insulating resin particles to the surface of the palladium layer through a chemical bond is preferable.
　（異方性導電材料）
　本発明に係る異方性導電材料は、本発明の導電性粒子と、バインダー樹脂とを含有する。 (Anisotropic conductive material)
The anisotropic conductive material according to the present invention contains the conductive particles of the present invention and a binder resin.
　上記バインダー樹脂は特に限定されない。バインダー樹脂として、一般的には絶縁性の樹脂が用いられる。バインダー樹脂としては、例えば、ビニル樹脂、熱可塑性樹脂、硬化性樹脂、熱可塑性ブロック共重合体又はエラストマー等が挙げられる。バインダー樹脂は、１種のみが用いられてもよく、２種以上が併用されてもよい。 The binder resin is not particularly limited. As the binder resin, generally an insulating resin is used. Examples of the binder resin include a vinyl resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer, or an elastomer. As for binder resin, only 1 type may be used and 2 or more types may be used together.
　上記ビニル樹脂としては、例えば、酢酸ビニル樹脂、アクリル樹脂又はスチレン樹脂等が挙げられる。上記熱可塑性樹脂としては、例えば、ポリオレフィン樹脂、エチレン－酢酸ビニル共重合体又はポリアミド樹脂等が挙げられる。上記硬化性樹脂としては、例えば、エポキシ樹脂、ウレタン樹脂、ポリイミド樹脂又は不飽和ポリエステル樹脂等が挙げられる。なお、上記硬化性樹脂は、常温硬化型樹脂、熱硬化型樹脂、光硬化型樹脂又は湿気硬化型樹脂であってもよい。上記硬化性樹脂は、硬化剤と併用されてもよい。上記熱可塑性ブロック共重合体としては、例えば、スチレン－ブタジエン－スチレンブロック共重合体、スチレン－イソプレン－スチレンブロック共重合体、スチレン－ブタジエン－スチレンブロック共重合体の水素添加物、又はスチレン－イソプレン－スチレンブロック共重合体の水素添加物等が挙げられる。上記エラストマーとしては、例えば、スチレン－ブタジエン共重合ゴム、又はアクリロニトリル－スチレンブロック共重合ゴム等が挙げられる。 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, polyamide resin, and the like. Examples of the curable resin include epoxy resins, urethane resins, polyimide resins, and unsaturated polyester resins. 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. Examples of the thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, or a styrene-isoprene. -Hydrogenated products of styrene block copolymers. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
　異方性導電材料は、導電性粒子及びバインダー樹脂の他に、例えば、充填剤、増量剤、軟化剤、可塑剤、重合触媒、硬化触媒、着色剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤又は難燃剤等の各種添加剤を含んでいてもよい。 Anisotropic conductive materials include, for example, fillers, extenders, softeners, plasticizers, polymerization catalysts, curing catalysts, colorants, antioxidants, thermal stabilizers, light stabilizers, in addition to conductive particles and binder resins. Various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent or a flame retardant may be contained.
　上記バインダー樹脂中に導電性粒子を分散させる方法は、従来公知の分散方法を用いることができ特に限定されない。上記バインダー樹脂中に導電性粒子を分散させる方法としては、例えば、バインダー樹脂中に導電性粒子を添加した後、プラネタリーミキサー等で混練して分散させる方法、導電性粒子を水又は有機溶剤中にホモジナイザー等を用いて均一に分散させた後、バインダー樹脂中へ添加し、プラネタリーミキサー等で混練して分散させる方法、又はバインダー樹脂を水又は有機溶剤等で希釈した後、導電性粒子を添加し、プラネタリーミキサー等で混練して分散させる方法等が挙げられる。 The method for dispersing the conductive particles in the binder resin may be any conventionally known dispersion method and is not particularly limited. Examples of the method for dispersing the conductive particles in the binder resin include, for example, a method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. The conductive particles are dispersed in water or an organic solvent. After uniformly dispersing using a homogenizer or the like, it is added to a binder resin and kneaded with a planetary mixer or the like, or after the binder resin is diluted with water or an organic solvent, the conductive particles are dispersed. The method of adding, kneading | mixing with a planetary mixer etc., and dispersing is mentioned.
　本発明の異方性導電材料は、異方性導電ペースト、異方性導電インク、異方性導電粘接着剤、異方性導電フィルム、又は異方性導電シート等として使用され得る。本発明の導電性粒子を含む異方性導電材料が、異方性導電フィルム又は異方性導電シート等のフィルム状の接着剤として使用される場合には、該導電性粒子を含むフィルム状の接着剤に、導電性粒子を含まないフィルム状の接着剤が積層されていてもよい。 The anisotropic conductive material of the present invention can be used as an anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, anisotropic conductive film, anisotropic conductive sheet or the like. When the anisotropic conductive material containing the conductive particles of the present invention is used as a film-like adhesive such as an anisotropic conductive film or an anisotropic conductive sheet, the film-like shape containing the conductive particles is used. A film-like adhesive that does not contain conductive particles may be laminated on the adhesive.
　（接続構造体）
　図３は、本発明の一実施形態に係る導電性粒子を用いた接続構造体を示す正面断面図である。 (Connection structure)
FIG. 3 is a front sectional view showing a connection structure using conductive particles according to an embodiment of the present invention.
　図３に示すように、接続構造体１１は、第１の接続対象部材としての回路基板１２と、第２の接続対象部材としての半導体チップ１４と、該回路基板１２と半導体チップ１４との電極１２ａ，１４ａ間を電気的に接続している接続部１３とを備える。接続部１３は、異方性導電フィルムにより形成されている。 As shown in FIG. 3, the connection structure 11 includes a circuit board 12 as a first connection target member, a semiconductor chip 14 as a second connection target member, and electrodes of the circuit board 12 and the semiconductor chip 14. 12a, and 14a are provided with the connection part 13 which has connected electrically. The connection part 13 is formed of an anisotropic conductive film.
　回路基板１２の上面に、複数の電極１２ａが設けられている。半導体チップ１４の下面に、複数の電極１４ａが設けられている。回路基板１２の上面に、導電性粒子１を含む異方性導電フィルムを介して、半導体チップ１４が積層されている。電極１２ａと電極１４ａとの間に、導電性粒子１を含む異方性導電フィルムにより形成された接続部１３が配置されている。導電性粒子１にかえて導電性粒子２１を用いてもよい。図３では、導電性粒子１は略図的に示されている。 A plurality of electrodes 12 a are provided on the upper surface of the circuit board 12. A plurality of electrodes 14 a are provided on the lower surface of the semiconductor chip 14. A semiconductor chip 14 is laminated on the upper surface of the circuit board 12 via an anisotropic conductive film containing the conductive particles 1. A connecting portion 13 formed of an anisotropic conductive film including the conductive particles 1 is disposed between the electrode 12a and the electrode 14a. Instead of the conductive particles 1, conductive particles 21 may be used. In FIG. 3, the conductive particles 1 are shown schematically.
　上記接続構造体としては、具体的には、回路基板上に、半導体チップ、コンデンサチップ又はダイオードチップ等の電子部品チップが搭載されており、該電子部品チップの電極が、回路基板上の電極と電気的に接続されている接続構造体等が挙げられる。回路基板としては、フレキシブルプリント基板等の様々なプリント基板、ガラス基板、又は金属箔が積層された基板等の様々な回路基板が挙げられる。 Specifically, as the connection structure, an electronic component chip such as a semiconductor chip, a capacitor chip or a diode chip is mounted on a circuit board, and the electrode of the electronic component chip is connected to an electrode on the circuit board. Examples include electrically connected structures. As a circuit board, various printed circuit boards, such as various printed circuit boards, such as a flexible printed circuit board, a glass substrate, or a board | substrate with which metal foil was laminated | stacked are mentioned.
　上記接続構造体の製造方法は特に限定されない。接続構造体の製造方法の一例としては、電子部品又は回路基板等の第１の接続対象部材と、電子部品又は回路基板等の第２の接続対象部材との間に上記異方性導電材料を配置して、積層体を得た後、該積層体を加熱、加圧する方法が挙げられる。 The manufacturing method of the connection structure is not particularly limited. As an example of a method for manufacturing a connection structure, the anisotropic conductive material is provided between a first connection target member such as an electronic component or a circuit board and a second connection target member such as an electronic component or a circuit board. A method of heating and pressurizing the laminated body after arranging and obtaining the laminated body is mentioned.
　以下、本発明について、実施例および比較例を挙げて具体的に説明する。本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited only to the following examples.
　（実施例１）
　（１）無電解ニッケルめっき工程
　平均粒子径４μｍのジビニルベンゼン樹脂粒子を、イオン吸着剤の１０重量％溶液により５分間処理し、次に硫酸パラジウム０．０１重量％水溶液により５分間処理した。その後、ジメチルアミンボランを加えて還元処理し、ろ過し、洗浄することにより、パラジウムが付着された樹脂粒子を得た。 Example 1
(1) Electroless nickel plating step Divinylbenzene resin particles having an average particle diameter of 4 μm were treated with a 10 wt% solution of an ion adsorbent for 5 minutes, and then treated with a 0.01 wt% palladium sulfate aqueous solution for 5 minutes. Thereafter, dimethylamine borane was added for reduction treatment, filtration, and washing to obtain resin particles to which palladium was attached.
　次に、イオン交換水５００ｍＬにコハク酸ナトリウムを溶解させたコハク酸ナトリウム１重量％溶液を調製した。この溶液にパラジウムが付着された樹脂粒子１０ｇを加え、混合し、スラリーを調製した。スラリーのｐＨを６．５に調整した。ニッケルめっき液として、硫酸ニッケル１０重量％、次亜リン酸ナトリウム１０重量％、水酸化ナトリウム４重量％及びコハク酸ナトリウム２０重量％を含む前期ニッケル溶液を調製した。ｐＨ６．５に調整された上記スラリーを８０℃に加温した後、スラリーに前期ニッケル溶液を連続的に滴下し、２０分間攪拌することによりめっき反応を進行させた。水素が発生しなくなったことを確認し、めっき反応を終了した。 Next, a 1% by weight sodium succinate solution in which sodium succinate was dissolved in 500 mL of ion-exchanged water was prepared. To this solution, 10 g of resin particles with palladium attached were added and mixed to prepare a slurry. The pH of the slurry was adjusted to 6.5. As a nickel plating solution, an initial nickel solution containing 10% by weight of nickel sulfate, 10% by weight of sodium hypophosphite, 4% by weight of sodium hydroxide and 20% by weight of sodium succinate was prepared. The slurry adjusted to pH 6.5 was heated to 80 ° C., and then the nickel solution was continuously added dropwise to the slurry and stirred for 20 minutes to advance the plating reaction. After confirming that hydrogen was no longer generated, the plating reaction was completed.
　次に、硫酸ニッケル２０重量％、次亜リン酸ナトリウム２０重量％及び水酸化ナトリウム５重量％を含む後期ニッケル溶液を調製した。前期ニッケル溶液によるめっき反応を終えた溶液に、後期ニッケル溶液を連続的に滴下し、１時間攪拌することによりめっき反応を進行させた。このようにして、樹脂粒子の表面にニッケル層を形成し、ニッケルめっき粒子を得た。なお、ニッケル層の厚みは、０．１μｍであった。 Next, a late nickel solution containing 20% by weight of nickel sulfate, 20% by weight of sodium hypophosphite and 5% by weight of sodium hydroxide was prepared. The late nickel solution was continuously added dropwise to the solution that had undergone the plating reaction with the nickel solution, and the plating reaction was allowed to proceed by stirring for 1 hour. In this way, a nickel layer was formed on the surface of the resin particles to obtain nickel plated particles. The nickel layer had a thickness of 0.1 μm.
　（２）無電解パラジウムめっき工程
　得られたニッケルめっき粒子１０ｇを、超音波処理機により、イオン交換水５００ｍＬに分散させ、粒子懸濁液を得た。この懸濁液を５０℃で攪拌しながら、硫酸パラジウム０．０２ｍｏｌ／Ｌ、錯化剤としてエチレンジアミン０．０４ｍｏｌ／Ｌ、還元剤として蟻酸ナトリウム０．０６ｍｏｌ／Ｌ及び結晶調整剤を含むｐＨ１０．０の無電解メッキ液を徐々に添加し、無電解パラジウムめっきを行った。パラジウム層の厚みが０．０３μｍになった時点で無電解パラジウムめっきを終了した。次に、洗浄し、真空乾燥することにより、ニッケル層の表面にパラジウム層が形成された導電性粒子を得た。 (2) Electroless palladium plating step 10 g of the obtained nickel-plated particles were dispersed in 500 mL of ion-exchanged water using an ultrasonic treatment machine to obtain a particle suspension. While stirring the suspension at 50 ° C., 0.02 mol / L of palladium sulfate, 0.04 mol / L of ethylenediamine as a complexing agent, 0.06 mol / L of sodium formate as a reducing agent, and pH 10.0 containing a crystal modifier. The electroless plating solution was gradually added to perform electroless palladium plating. When the thickness of the palladium layer reached 0.03 μm, the electroless palladium plating was finished. Next, by washing and vacuum drying, conductive particles having a palladium layer formed on the surface of the nickel layer were obtained.
　（実施例２）
　（１）無電解ニッケルめっき工程
　平均粒子径４μｍのジビニルベンゼン樹脂粒子を、イオン吸着剤の１０重量％溶液により５分間処理し、次に硫酸パラジウム０．０１重量％水溶液により５分間処理した。その後、ジメチルアミンボランを加えて還元処理し、ろ過し、洗浄することにより、パラジウムが付着された樹脂粒子を得た。 (Example 2)
(1) Electroless nickel plating step Divinylbenzene resin particles having an average particle diameter of 4 μm were treated with a 10 wt% solution of an ion adsorbent for 5 minutes, and then treated with a 0.01 wt% palladium sulfate aqueous solution for 5 minutes. Thereafter, dimethylamine borane was added for reduction treatment, filtration, and washing to obtain resin particles to which palladium was attached.
　次に、イオン交換水５００ｍＬにコハク酸ナトリウムを溶解させたコハク酸ナトリウム１重量％溶液を調製した。この溶液にパラジウムが付着された樹脂粒子１０ｇを加え、混合し、スラリーを調製した。スラリーのｐＨを９．０に調整した。ニッケルめっき液として、硫酸ニッケル１０重量％、次亜リン酸ナトリウム１０重量％、水酸化ナトリウム４重量％及びコハク酸ナトリウム２０重量％を含む前期ニッケル溶液を調製した。ｐＨ９．０に調整された上記スラリーを８０℃に加温した後、スラリーに前期ニッケル溶液を連続的に滴下し、２０分間攪拌することによりめっき反応を進行させた。水素が発生しなくなったことを確認し、めっき反応を終了した。 Next, a 1% by weight sodium succinate solution in which sodium succinate was dissolved in 500 mL of ion-exchanged water was prepared. To this solution, 10 g of resin particles with palladium attached were added and mixed to prepare a slurry. The pH of the slurry was adjusted to 9.0. As a nickel plating solution, an initial nickel solution containing 10% by weight of nickel sulfate, 10% by weight of sodium hypophosphite, 4% by weight of sodium hydroxide and 20% by weight of sodium succinate was prepared. The slurry adjusted to pH 9.0 was heated to 80 ° C., and then the nickel solution was continuously added dropwise to the slurry and stirred for 20 minutes to advance the plating reaction. After confirming that hydrogen was no longer generated, the plating reaction was completed.
　次に、硫酸ニッケル２０重量％、次亜リン酸ナトリウム２０重量％及び水酸化ナトリウム１５重量％を含む後期ニッケル溶液を調製した。前期ニッケル溶液によるめっき反応を終えた溶液に、後期ニッケル溶液を連続的に滴下し、１時間攪拌することによりめっき反応を進行させた。このようにして、樹脂粒子の表面にニッケル層を形成し、ニッケルめっき粒子を得た。なお、ニッケル層の厚みは、０．１μｍであった。 Next, a late nickel solution containing 20% by weight of nickel sulfate, 20% by weight of sodium hypophosphite and 15% by weight of sodium hydroxide was prepared. The late nickel solution was continuously added dropwise to the solution that had finished the plating reaction with the previous nickel solution, and the plating reaction was allowed to proceed by stirring for 1 hour. In this way, a nickel layer was formed on the surface of the resin particles to obtain nickel plated particles. The nickel layer had a thickness of 0.1 μm.
　（２）無電解パラジウムめっき工程
　実施例１と同様にしてパラジウムめっき処理することにより、ニッケル層の表面にパラジウム層が形成された導電性粒子を得た。 (2) Electroless Palladium Plating Step By conducting palladium plating in the same manner as in Example 1, conductive particles having a palladium layer formed on the surface of the nickel layer were obtained.
　（実施例３）
　（１）無電解ニッケルめっき工程
　平均粒子径４μｍのジビニルベンゼン樹脂粒子を、イオン吸着剤の１０重量％溶液により５分間処理し、次に硫酸パラジウム０．０１重量％水溶液により５分間処理した。その後、ジメチルアミンボランを加えて還元処理し、ろ過し、洗浄することにより、パラジウムが付着された樹脂粒子を得た。 (Example 3)
(1) Electroless nickel plating step Divinylbenzene resin particles having an average particle diameter of 4 μm were treated with a 10 wt% solution of an ion adsorbent for 5 minutes, and then treated with a 0.01 wt% palladium sulfate aqueous solution for 5 minutes. Thereafter, dimethylamine borane was added for reduction treatment, filtration, and washing to obtain resin particles to which palladium was attached.
　次に、イオン交換水５００ｍＬにコハク酸ナトリウムを溶解させたコハク酸ナトリウム１重量％溶液を調製した。この溶液にパラジウムが付着された樹脂粒子１０ｇを加え、混合し、スラリーを調製した。スラリーのｐＨを４．５に調整した。ニッケルめっき液として、硫酸ニッケル１０重量％、次亜リン酸ナトリウム１０重量％、水酸化ナトリウム４重量％及びコハク酸ナトリウム２０重量％を含む前期ニッケル溶液を調製した。ｐＨ４．５に調整された上記スラリーを８０℃に加温した後、スラリーに前期ニッケル溶液を連続的に滴下し、２０分間攪拌することによりめっき反応を進行させた。水素が発生しなくなったことを確認し、めっき反応を終了した。 Next, a 1% by weight sodium succinate solution in which sodium succinate was dissolved in 500 mL of ion-exchanged water was prepared. To this solution, 10 g of resin particles with palladium attached were added and mixed to prepare a slurry. The pH of the slurry was adjusted to 4.5. As a nickel plating solution, an initial nickel solution containing 10% by weight of nickel sulfate, 10% by weight of sodium hypophosphite, 4% by weight of sodium hydroxide and 20% by weight of sodium succinate was prepared. The slurry adjusted to pH 4.5 was heated to 80 ° C., and then the nickel solution was continuously added dropwise to the slurry and stirred for 20 minutes to advance the plating reaction. After confirming that hydrogen was no longer generated, the plating reaction was completed.
　次に、硫酸ニッケル２０重量％、次亜リン酸ナトリウム３０重量％及び水酸化ナトリウム５重量％を含む後期ニッケル溶液を調製した。前期ニッケル溶液によるめっき反応を終えた溶液に、後期ニッケル溶液を連続的に滴下し、１時間攪拌することによりめっき反応を進行させた。このようにして、樹脂粒子の表面にニッケル層を形成し、ニッケルめっき粒子を得た。なお、ニッケル層の厚みは、０．１μｍであった。 Next, a late nickel solution containing 20% by weight of nickel sulfate, 30% by weight of sodium hypophosphite and 5% by weight of sodium hydroxide was prepared. The late nickel solution was continuously added dropwise to the solution that had finished the plating reaction with the previous nickel solution, and the plating reaction was allowed to proceed by stirring for 1 hour. In this way, a nickel layer was formed on the surface of the resin particles to obtain nickel plated particles. The nickel layer had a thickness of 0.1 μm.
　（２）無電解パラジウムめっき工程
　実施例１と同様にしてパラジウムめっき処理することにより、ニッケル層の表面にパラジウム層が形成された導電性粒子を得た。 (2) Electroless Palladium Plating Step By conducting palladium plating in the same manner as in Example 1, conductive particles having a palladium layer formed on the surface of the nickel layer were obtained.
　（実施例４）
　（１）無電解ニッケルめっき工程（ニッケル層の表面に突起を形成する工程）
　１－１）パラジウム付着工程
　平均粒子径４μｍのジビニルベンゼン樹脂粒子１０ｇを用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を８重量％含むパラジウム触媒化液１００ｍＬ中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。ｐＨ６の０．５重量％ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着された樹脂粒子を得た。 Example 4
(1) Electroless nickel plating step (step of forming protrusions on the surface of the nickel layer)
1-1) Palladium adhesion step 10 g of divinylbenzene resin particles having an average particle diameter of 4 μm were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash | cleaned. Resin particles were added to 0.5 wt% dimethylamine borane solution at pH 6 to obtain resin particles to which palladium was attached.
　１－２）芯物質付着工程
　パラジウムが付着された樹脂粒子をイオン交換水３００ｍＬ中で３分間攪拌し、分散させ、分散液を得た。次に、金属ニッケル粒子スラリー（三井金属社製「２０２０ＳＵＳ」、平均粒子径２００ｎｍ）１ｇを３分間かけて上記分散液に添加し、芯物質が付着された樹脂粒子を得た。 1-2) Core substance attaching step The resin particles to which palladium was attached were stirred and dispersed in 300 mL of ion-exchanged water for 3 minutes to obtain a dispersion. Next, 1 g of a metallic nickel particle slurry (“2020SUS” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter 200 nm) was added to the dispersion over 3 minutes to obtain resin particles to which a core substance was adhered.
　１－３）無電解ニッケルめっき工程
　芯物質が付着された樹脂粒子にイオン交換水５００ｍＬを加え、樹脂粒子を十分に分散させて懸濁液を得た。この懸濁液を攪拌しながら、硫酸ニッケル６水和物５０ｇ／Ｌ、次亜リン酸ナトリウム１水和物４０ｇ／Ｌ及びクエン酸５０ｇ／Ｌを含むｐＨ５．０の無電解ニッケルめっき液を徐々に添加し、無電解ニッケルめっきを行った。このようにして、樹脂粒子の表面にニッケル層を形成し、表面に突起を有するニッケルめっき粒子を得た。なお、ニッケル層の厚みは、０．１μｍであった。 1-3) Electroless Nickel Plating Step 500 mL of ion-exchanged water was added to the resin particles to which the core substance was adhered, and the resin particles were sufficiently dispersed to obtain a suspension. While stirring this suspension, an electroless nickel plating solution having a pH of 5.0 containing nickel sulfate hexahydrate 50 g / L, sodium hypophosphite monohydrate 40 g / L and citric acid 50 g / L was gradually added. And electroless nickel plating. In this way, a nickel layer was formed on the surface of the resin particles, and nickel plated particles having protrusions on the surface were obtained. The nickel layer had a thickness of 0.1 μm.
　（２）無電解パラジウムめっき工程
　得られたニッケルめっき粒子１０ｇを用いて、実施例１と同様の無電解パラジウムめっき工程を行うことにより、ニッケル層の表面にパラジウム層が形成された導電性粒子を得た。得られた導電性粒子は、表面に突起を有していた。 (2) Electroless palladium plating step Conductive particles having a palladium layer formed on the surface of the nickel layer are obtained by performing the same electroless palladium plating step as in Example 1 using 10 g of the obtained nickel plating particles. Obtained. The obtained conductive particles had protrusions on the surface.
　（実施例５）
　ジビニルベンゼン樹脂粒子を、１，４－ブタンジオールジアクリレートと、テトラメチロールメタンテトラアクリレートとの共重合樹脂粒子（１，４－ブタンジオールジアクリレート：テトラメチロールメタンテトラアクリレート＝９５重量％：５重量％）に変更したこと以外は、実施例４と同様にして導電性粒子を得た。得られた導電性粒子は、表面に突起を有していた。 (Example 5)
Divinylbenzene resin particles are copolymerized resin particles of 1,4-butanediol diacrylate and tetramethylol methane tetraacrylate (1,4-butanediol diacrylate: tetramethylol methane tetraacrylate = 95 wt%: 5 wt% The conductive particles were obtained in the same manner as in Example 4 except that the change was made to). The obtained conductive particles had protrusions on the surface.
　（実施例６）
　（１）絶縁樹脂粒子の作製
　４ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブが取り付けられた１０００ｍＬのセパラブルフラスコに、メタクリル酸メチル１００ｍｍｏｌと、Ｎ，Ｎ，Ｎ－トリメチル－Ｎ－２－メタクリロイルオキシエチルアンモニウムクロライド１ｍｍｏｌと、２，２’－アゾビス（２－アミジノプロパン）二塩酸塩１ｍｍｏｌとを含むモノマー組成物を固形分率が５重量％となるようにイオン交換水に秤取した後、２００ｒｐｍで攪拌し、窒素雰囲気下７０℃で２４時間重合を行った。反応終了後、凍結乾燥して、表面にアンモニウム基を有し、平均粒子径２２０ｎｍ及びＣＶ値１０％の絶縁樹脂粒子を得た。 (Example 6)
(1) Production of insulating resin particles In a 1000 mL separable flask equipped with a four-neck separable cover, a stirring blade, a three-way cock, a condenser tube and a temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, freeze drying was performed to obtain insulating resin particles having an ammonium group on the surface, an average particle diameter of 220 nm, and a CV value of 10%.
　絶縁樹脂粒子を超音波照射下でイオン交換水に分散させ、絶縁樹脂粒子の１０重量％水分散液を得た。 The insulating resin particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating resin particles.
　実施例５で得られた導電性粒子１０ｇをイオン交換水５００ｍＬに分散させ、絶縁樹脂粒子の水分散液４ｇを添加し、室温で６時間攪拌した。３μｍのメッシュフィルターでろ過した後、更にメタノールで洗浄し、乾燥し、絶縁樹脂粒子が付着した導電性粒子を得た。 10 g of the conductive particles obtained in Example 5 were dispersed in 500 mL of ion exchange water, 4 g of an aqueous dispersion of insulating resin particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 μm mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating resin particles attached thereto.
　走査電子顕微鏡（ＳＥＭ）により観察したところ、導電性粒子の表面に絶縁樹脂粒子による被覆層が１層のみ形成されていた。画像解析により導電性粒子の中心より２．５μｍの面積に対する絶縁樹脂粒子の被覆面積（即ち絶縁樹脂粒子の粒子径の投影面積）を算出したところ、被覆率は３０％であった。 When observed with a scanning electron microscope (SEM), only one coating layer of insulating resin particles was formed on the surface of the conductive particles. When the coated area of the insulating resin particles (that is, the projected area of the particle diameter of the insulating resin particles) with respect to the area of 2.5 μm from the center of the conductive particles was calculated by image analysis, the coverage was 30%.
　（実施例７）
　ジビニルベンゼン樹脂粒子を、１，４－ブタンジオールジアクリレートと、テトラメチロールメタンテトラアクリレートとの共重合樹脂粒子（１，４－ブタンジオールジアクリレート：テトラメチロールメタンテトラアクリレート＝９５重量％：５重量％）に変更したこと以外は、実施例１と同様にして導電性粒子を得た。 (Example 7)
Divinylbenzene resin particles are copolymerized resin particles of 1,4-butanediol diacrylate and tetramethylol methane tetraacrylate (1,4-butanediol diacrylate: tetramethylol methane tetraacrylate = 95 wt%: 5 wt% The conductive particles were obtained in the same manner as in Example 1 except that the above was changed.
　（実施例８）
　実施例５で得られた導電性粒子を実施例１で得られた導電性粒子に変更したこと以外は、実施例６と同様にして絶縁樹脂粒子が付着した導電性粒子を得た。 (Example 8)
Except having changed the electroconductive particle obtained in Example 5 into the electroconductive particle obtained in Example 1, it carried out similarly to Example 6, and obtained the electroconductive particle to which the insulating resin particle adhered.
　（実施例９）
　実施例５で得られた導電性粒子を実施例４で得られた導電性粒子に変更したこと以外は、実施例６と同様にして絶縁樹脂粒子が付着した導電性粒子を得た。 Example 9
Except having changed the electroconductive particle obtained in Example 5 into the electroconductive particle obtained in Example 4, it carried out similarly to Example 6, and obtained the electroconductive particle to which the insulating resin particle adhered.
　（実施例１０）
　実施例５で得られた導電性粒子を実施例７で得られた導電性粒子に変更したこと以外は、実施例６と同様にして絶縁樹脂粒子が付着した導電性粒子を得た。 (Example 10)
Except having changed the electroconductive particle obtained in Example 5 into the electroconductive particle obtained in Example 7, it carried out similarly to Example 6, and obtained the electroconductive particle to which the insulating resin particle adhered.
　（実施例１１）
（１）無電解ニッケルめっき工程
　実施例１の無電解ニッケルめっき工程と同様にして樹脂粒子の表面にニッケル層が形成されたニッケルめっき粒子を得た。 (Example 11)
(1) Electroless nickel plating step In the same manner as in the electroless nickel plating step of Example 1, nickel plated particles having a nickel layer formed on the surface of the resin particles were obtained.
（２）無電解パラジウムめっき工程
　錯化剤としてエチレンジアミン０．０３５ｍｏｌ／Ｌ、還元剤として蟻酸ナトリウム０．０５ｍｏｌ／Ｌ及び結晶調整剤を含むｐＨ９．０の無電解メッキ液に変更したこと以外は、実施例１と同様にしてニッケル層の表面にパラジウム層が形成された導電性粒子を得た。 (2) Electroless palladium plating step Except for changing to an electroless plating solution having a pH of 9.0 containing 0.035 mol / L of ethylenediamine as a complexing agent, 0.05 mol / L of sodium formate as a reducing agent and a crystal modifier, In the same manner as in Example 1, conductive particles having a palladium layer formed on the surface of the nickel layer were obtained.
　（比較例１）
　無電解パラジウムめっき工程において、硫酸パラジウム０．０２ｍｏｌ／Ｌ、錯化剤としてエチレンジアミン０．０４ｍｏｌ／Ｌ、還元剤として蟻酸ナトリウム０．０６ｍｏｌ／Ｌ及び結晶調整剤を含むｐＨ１０．０の無電解メッキ液を、硫酸パラジウム０．０２ｍｏｌ／Ｌ、錯化剤としてエチレンジアミン０．０４ｍｏｌ／Ｌ、還元剤として次亜リン酸ナトリウム０．０９ｍｏｌ／Ｌ及び結晶調整剤を含むｐＨ６．５の無電解メッキ液に変更したこと以外は実施例１と同様にして、樹脂粒子の表面にニッケル層が形成されており、かつニッケル層の表面にパラジウム層が形成されている導電性粒子を得た。 (Comparative Example 1)
In the electroless palladium plating process, electroless plating solution having a pH of 10.0 containing 0.02 mol / L of palladium sulfate, 0.04 mol / L of ethylenediamine as a complexing agent, 0.06 mol / L of sodium formate as a reducing agent, and a crystal modifier. Was changed to an electroless plating solution of pH 6.5 containing 0.02 mol / L of palladium sulfate, 0.04 mol / L of ethylenediamine as a complexing agent, 0.09 mol / L of sodium hypophosphite as a reducing agent and a crystal modifier. Except that, conductive particles having a nickel layer formed on the surface of the resin particles and a palladium layer formed on the surface of the nickel layer were obtained in the same manner as in Example 1.
　（比較例２）
　無電解ニッケルめっき工程において、ｐＨを調製する際にｐＨを７．５に調整したこと、並びに硫酸ニッケル１０重量％、次亜リン酸ナトリウム１０重量％、水酸化ナトリウム４重量％及びコハク酸ナトリウム２０重量％を含む前期ニッケル溶液を、硫酸ニッケル１０重量％、次亜リン酸ナトリウム６重量％、水酸化ナトリウム４重量％及びコハク酸ナトリウム２０重量％を含む前期ニッケル溶液に変更したこと以外は実施例１と同様にして、樹脂粒子の表面にニッケル層が形成されており、かつニッケル層の表面にパラジウム層が形成されている導電性粒子を得た。 (Comparative Example 2)
In the electroless nickel plating step, the pH was adjusted to 7.5 when adjusting the pH, and nickel sulfate 10 wt%, sodium hypophosphite 10 wt%, sodium hydroxide 4 wt%, and sodium succinate 20 Example 1 except that the nickel solution containing 10% by weight was changed to a nickel solution containing 10% by weight nickel sulfate, 6% by weight sodium hypophosphite, 4% by weight sodium hydroxide and 20% by weight sodium succinate. In the same manner as in Example 1, conductive particles having a nickel layer formed on the surface of the resin particles and a palladium layer formed on the surface of the nickel layer were obtained.
（比較例３）
　無電解ニッケルめっき工程において、スラリーのｐＨを４．５に調整したこと、並びに硫酸ニッケル１０重量％、次亜リン酸ナトリウム１０重量％、水酸化ナトリウム４重量％及びコハク酸ナトリウム２０重量％を含む前期ニッケル溶液を、硫酸ニッケル１０重量％、次亜リン酸ナトリウム３０重量％、水酸化ナトリウム４重量％及びコハク酸ナトリウム２０重量％を含む前期ニッケル溶液に変更したこと以外は実施例１と同様にして、樹脂粒子の表面にニッケル層が形成されており、かつニッケル層の表面にパラジウム層が形成されている導電性粒子を得た。 (Comparative Example 3)
In the electroless nickel plating step, the pH of the slurry was adjusted to 4.5, and 10% by weight of nickel sulfate, 10% by weight of sodium hypophosphite, 4% by weight of sodium hydroxide and 20% by weight of sodium succinate were included. Example 1 was the same as Example 1 except that the nickel solution was changed to a nickel solution containing 10% by weight nickel sulfate, 30% by weight sodium hypophosphite, 4% by weight sodium hydroxide and 20% by weight sodium succinate. Thus, conductive particles having a nickel layer formed on the surface of the resin particles and a palladium layer formed on the surface of the nickel layer were obtained.
　（比較例４）
（１）無電解ニッケルめっき工程
　実施例１の無電解ニッケルめっき工程と同様にして樹脂粒子の表面にニッケル層が形成されたニッケルめっき粒子を得た。 (Comparative Example 4)
(1) Electroless nickel plating step In the same manner as in the electroless nickel plating step of Example 1, nickel plated particles having a nickel layer formed on the surface of the resin particles were obtained.
（２）無電解パラジウムめっき工程
　錯化剤としてエチレンジアミン０．０３０ｍｏｌ／Ｌ、還元剤として蟻酸ナトリウム０．０４ｍｏｌ／Ｌ及び結晶調整剤を含むｐＨ８．５の無電解メッキ液に変更したこと以外は、実施例１と同様にしてニッケル層の表面にパラジウム層が形成された導電性粒子を得た。 (2) Electroless palladium plating step Except for changing to an electroless plating solution having a pH of 8.5 containing ethylenediamine 0.030 mol / L as a complexing agent, sodium formate 0.04 mol / L as a reducing agent and a crystal modifier, In the same manner as in Example 1, conductive particles having a palladium layer formed on the surface of the nickel layer were obtained.
　（評価）
　（１）ニッケル層のリンの含有率
　集束イオンビームを用いて、得られた導電性粒子の薄膜切片を作製した。透過型電子顕微鏡ＦＥ－ＴＥＭ（日本電子社製「ＪＥＭ－２０１０ＦＥＦ」）を用いて、エネルギー分散型Ｘ線分析装置（ＥＤＳ）により、ニッケル層のリンの含有率を測定した。同様に、任意の導電性粒子１０個のニッケル層のリンの含有率を測定し、平均値を算出した。 (Evaluation)
(1) Phosphorus content of nickel layer Thin film slices of the obtained conductive particles were prepared using a focused ion beam. Using a transmission electron microscope FE-TEM (“JEM-2010FEF” manufactured by JEOL Ltd.), the phosphorus content of the nickel layer was measured by an energy dispersive X-ray analyzer (EDS). Similarly, the phosphorus content of the nickel layer of 10 arbitrary conductive particles was measured, and the average value was calculated.
　（２）パラジウム層のパラジウムの含有率
　集束イオンビームを用いて、得られた導電性粒子の薄膜切片を作製した。透過型電子顕微鏡ＦＥ－ＴＥＭ（日本電子社製「ＪＥＭ－２０１０ＦＥＦ」）を用いて、エネルギー分散型Ｘ線分析装置（ＥＤＳ）により、パラジウム層のパラジウムの含有率を測定した。同様に、任意の導電性粒子１０個のパラジウム層のパラジウムの含有率を測定し、平均値を算出した。 (2) Palladium Content of Palladium Layer Using a focused ion beam, a thin film slice of the obtained conductive particles was prepared. Using a transmission electron microscope FE-TEM (“JEM-2010FEF” manufactured by JEOL Ltd.), the content of palladium in the palladium layer was measured with an energy dispersive X-ray analyzer (EDS). Similarly, the palladium content of the palladium layer of 10 arbitrary conductive particles was measured, and the average value was calculated.
　（３）接続抵抗
　Ｌ／Ｓが１００μｍ／１００μｍの銅電極が形成された２枚の基板を用意した。また、実施例及び比較例で得られた導電性粒子１０重量部と、バインダー樹脂としてのエポキシ樹脂（三井化学社製「ストラクトボンドＸＮ－５Ａ」）８５重量部と、イミダゾール型硬化剤５重量部とを含む異方性導電ペーストを用意した。 (3) Connection resistance Two substrates on which copper electrodes with L / S of 100 μm / 100 μm were formed were prepared. In addition, 10 parts by weight of the conductive particles obtained in Examples and Comparative Examples, 85 parts by weight of an epoxy resin (“Stractbond XN-5A” manufactured by Mitsui Chemicals) as a binder resin, and 5 parts by weight of an imidazole type curing agent An anisotropic conductive paste containing was prepared.
　基板の上面に異方性導電ペーストを導電性粒子が銅電極に接触するように塗布した後、他の基板を銅電極が導電性粒子に接触するように積層し、圧着し、積層体を得た。その後、積層体を１８０℃で１分間加熱することにより、異方性導電ペーストを硬化させ、接続構造体を得た。 After applying the anisotropic conductive paste on the upper surface of the substrate so that the conductive particles are in contact with the copper electrode, the other substrate is laminated so that the copper electrode is in contact with the conductive particles, and is bonded to obtain a laminate. It was. Then, the anisotropic conductive paste was hardened by heating a laminated body at 180 degreeC for 1 minute, and the connection structure was obtained.
　得られた接続構造体の対向する電極間の接続抵抗を四端子法により測定し、得られた測定値を初期接続抵抗とした。 The connection resistance between the opposing electrodes of the obtained connection structure was measured by the four-terminal method, and the obtained measurement value was used as the initial connection resistance.
　次に、得られた接続構造体を８５℃及び湿度８５％の条件で１００時間放置した。放置後の接続構造体の電極間の接続抵抗を四端子法により測定し、得られた測定値を高温高湿試験後の接続抵抗とした。 Next, the obtained connection structure was left for 100 hours under the conditions of 85 ° C. and humidity 85%. The connection resistance between the electrodes of the connection structure after being allowed to stand was measured by the four-terminal method, and the obtained measured value was used as the connection resistance after the high temperature and high humidity test.
　（４）絶縁抵抗
　図４に示すように、銅電極の表面に、ニッケルめっき層及び金めっき層が順次形成された、Ｌ／Ｓが２０μｍ／２０μｍのくし歯電極銅パターン３１，３２が形成された基板を用意した。また、実施例及び比較例で得られた導電性粒子１０重量部と、バインダー樹脂としてのエポキシ樹脂（三井化学社製「ストラクトボンドＸＮ－５Ａ」）８５重量部と、イミダゾール型硬化剤５重量部とを含む異方性導電ペーストを用意した。 (4) Insulation resistance As shown in FIG. 4, comb-shaped electrode copper patterns 31 and 32 having a L / S of 20 μm / 20 μm, in which a nickel plating layer and a gold plating layer are sequentially formed, are formed on the surface of the copper electrode. A prepared substrate was prepared. In addition, 10 parts by weight of the conductive particles obtained in Examples and Comparative Examples, 85 parts by weight of an epoxy resin (“Stractbond XN-5A” manufactured by Mitsui Chemicals) as a binder resin, and 5 parts by weight of an imidazole type curing agent An anisotropic conductive paste containing was prepared.
　基板の銅パターン３１，３２の上面に異方性導電ペーストを塗布した後、アルカリフリーガラス板を積層し、圧着し、導電性粒子を銅パターン３１，３２に接触させた。アルカリフリーガラス板を積層した状態で、１８０℃で１分間加熱することにより、異方性導電ペーストを硬化させ、接続構造体を得た。 An anisotropic conductive paste was applied to the upper surfaces of the copper patterns 31 and 32 of the substrate, and then an alkali-free glass plate was laminated and pressed, and the conductive particles were brought into contact with the copper patterns 31 and 32. In the state which laminated | stacked the alkali free glass plate, the anisotropic conductive paste was hardened by heating at 180 degreeC for 1 minute, and the connection structure was obtained.
　得られた接続構造体の隣接する電極間の絶縁抵抗を四端子法により測定し、得られた測定値を初期絶縁抵抗とした。 The insulation resistance between the adjacent electrodes of the obtained connection structure was measured by a four-terminal method, and the obtained measurement value was used as the initial insulation resistance.
　次に、得られた接続構造体を、電極間に５０Ｖのバイアス電圧を印加しながら、８５℃及び湿度８５％の条件で１０００時間放置した。放置後の接続構造体の隣接する電極間の絶縁抵抗を四端子法により測定し、得られた測定値を高温高湿試験後の絶縁抵抗とした。 Next, the obtained connection structure was allowed to stand for 1000 hours under conditions of 85 ° C. and 85% humidity while applying a bias voltage of 50 V between the electrodes. The insulation resistance between the adjacent electrodes of the connection structure after being allowed to stand was measured by the four-terminal method, and the obtained measurement value was taken as the insulation resistance after the high temperature and high humidity test.
　結果を下記の表１に示す。 The results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　１…導電性粒子
　２…基材粒子
　２ａ…表面
　３…ニッケル層
　３ａ…表面
　４…パラジウム層
　４ａ…表面
　１１…接続構造体
　１２…回路基板
　１２ａ…電極
　１３…接続部
　１４…半導体チップ
　１４ａ…電極
　２１…導電性粒子
　２１ａ…表面
　２２…ニッケル層
　２２ａ…表面
　２３…パラジウム層
　２３ａ…表面
　２４…芯物質
　２５…突起
　２６…絶縁性樹脂
　３１，３２…くし歯電極銅パターン
  DESCRIPTION OF SYMBOLS 1 ... Conductive particle 2 ... Base particle 2a ... Surface 3 ... Nickel layer 3a ... Surface 4 ... Palladium layer 4a ... Surface 11 ... Connection structure 12 ... Circuit board 12a ... Electrode 13 ... Connection part 14 ... Semiconductor chip 14a ... Electrode DESCRIPTION OF SYMBOLS 21 ... Conductive particle 21a ... Surface 22 ... Nickel layer 22a ... Surface 23 ... Palladium layer 23a ... Surface 24 ... Core substance 25 ... Projection 26 ... Insulating resin 31, 32 ... Copper electrode copper pattern

Claims (7)

  1. 基材粒子と、該基材粒子の表面に形成されたニッケル層と、該ニッケル層の表面に形成されたパラジウム層とを備え、
    　前記ニッケル層のリンの含有率が５～１５重量％の範囲内であり、かつ前記パラジウム層のパラジウムの含有率が９６重量％以上である、導電性粒子。     A substrate particle, a nickel layer formed on the surface of the substrate particle, and a palladium layer formed on the surface of the nickel layer,
    Conductive particles in which the phosphorus content of the nickel layer is in the range of 5 to 15% by weight and the palladium content of the palladium layer is 96% by weight or more.
  2. 　表面に突起を有する、請求項１に記載の導電性粒子。 The conductive particle according to claim 1, wherein the surface has a protrusion.
  3. 　前記パラジウム層の外側の表面に突起を有する、請求項１に記載の導電性粒子。 The electroconductive particle according to claim 1, which has a protrusion on the outer surface of the palladium layer.
  4. 　前記パラジウム層の表面に付着された絶縁性樹脂をさらに備える、請求項１～３のいずれか１項に記載の導電性粒子。 The conductive particle according to any one of claims 1 to 3, further comprising an insulating resin attached to a surface of the palladium layer.
  5. 　前記絶縁性樹脂が絶縁樹脂粒子である、請求項４に記載の導電性粒子。 The conductive particle according to claim 4, wherein the insulating resin is an insulating resin particle.
  6. 　請求項１～５のいずれか１項に記載の導電性粒子と、バインダー樹脂とを含む、異方性導電材料。 An anisotropic conductive material comprising the conductive particles according to any one of claims 1 to 5 and a binder resin.
  7. 　第１の接続対象部材と、第２の接続対象部材と、該第１，第２の接続対象部材を電気的に接続している接続部とを備え、
    　前記接続部が請求項１～５のいずれか１項に記載の導電性粒子又は該導電性粒子とバインダー樹脂とを含む異方性導電材料により形成されている、接続構造体。     A first connection target member, a second connection target member, and a connection part that electrically connects the first and second connection target members;
    A connection structure in which the connection portion is formed of the conductive particles according to any one of claims 1 to 5 or an anisotropic conductive material containing the conductive particles and a binder resin.
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