JP5548053B2 - Conductive particles with insulating particles, method for producing conductive particles with insulating particles, anisotropic conductive material, and connection structure - Google Patents

Description

  The present invention uses, for example, conductive particles with insulating particles that can be used for electrical connection between electrodes, a method for producing the conductive particles with insulating particles, and the conductive particles with insulating particles. The present invention relates to an anisotropic conductive material and a connection structure.

  Anisotropic conductive materials such as anisotropic conductive pastes, anisotropic conductive inks, anisotropic conductive adhesives, anisotropic conductive films and anisotropic conductive sheets are widely known. In these 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. For example, after disposing an anisotropic conductive material between the electrode of the IC chip and the electrode of the circuit board, these electrodes can be electrically connected by heating and pressing.

  As an example of the conductive particles, the following Patent Document 1 discloses conductive with insulating particles having conductive particles and insulating particles fixed to the surface of the conductive particles and having adhesive properties. Particles are disclosed. The insulating particles include hard particles and a polymer resin layer covering the surfaces of the hard particles. Here, a physical / mechanical hybridization method is used as an immobilization method in order to immobilize the insulating particles on the surface of the conductive particles.

  Patent Document 2 below includes conductive particles having a polar group on at least a part of a surface, and an insulating material that covers at least a part of the surface of the conductive particles and includes insulating particles. A conductive particle with insulating particles is disclosed. Specifically, the insulating material includes a polymer electrolyte that can adsorb the polar group, and inorganic oxide particles that can adsorb the polymer electrolyte. The inorganic oxide particles are insulating particles.

Special table 2007-537570 gazette JP 2008-120990 A

  In the conventional conductive particles with insulating particles as described in Patent Documents 1 and 2, the insulating particles are easily detached from the surface of the conductive particles. For example, when the conductive particles with insulating particles are dispersed in the binder resin, the insulating particles may be easily detached from the surface of the conductive particles.

  In particular, as described in Patent Document 1, when a physical / mechanical hybridization method is used to immobilize the insulating particles on the surface of the conductive particles, the insulating particles are made of conductive particles. Easily detached from the surface.

  Furthermore, when the physical / mechanical hybridization method is used, the polymer resin layer of the insulating particles adheres to a portion other than the portion to which the insulating particles adhere on the surface of the conductive particles, There is also a problem that the conductivity is impaired after the connection between the electrodes.

  It is an object of the present invention to provide conductive particles with insulating particles that can hardly improve the reliability of conduction when the insulating particles are not easily detached from the surface of the conductive particles, and thus are used for connection between electrodes. It is providing the anisotropic conductive material and connection structure using the manufacturing method of the electroconductive particle with an electroconductive particle, and this electroconductive particle with an insulating particle.

  According to a wide aspect of the present invention, it comprises conductive particles having a conductive layer on at least a surface thereof, and insulating particles attached to the surface of the conductive particles, the insulating particles comprising an insulating particle body and A portion that covers at least a part of the surface of the insulating particle main body and that is formed of a polymer compound, to which the insulating particles are attached on the surface of the conductive particles. Conductive particles with insulating particles, in which the polymer compound is not attached to other portions, are provided.

  The conductive particles with insulating particles to which the high molecular compound is not attached to a portion other than the portion to which the insulating particles are attached on the surface of the conductive particles are those other than the hybridization method. It is obtained by attaching by a method.

  According to another broad aspect of the present invention, the method includes conductive particles having a conductive layer on at least a surface thereof, and insulating particles attached to the surface of the conductive particles, the insulating particles being insulating particles. A body and a layer that covers at least a part of the surface of the insulating particle body and is formed of a polymer compound, and the insulating particles are not attached by a hybridization method; Conductive particles with insulating particles are provided.

  In the case where the insulating particles are not attached by the hybridization method, the insulating material in which the high molecular compound is not attached to a portion other than the portion to which the insulating particles are attached on the surface of the conductive particles. Conductive particles with conductive particles are obtained.

  On the specific situation with the electroconductive particle with an insulating particle which concerns on this invention, the said insulating particle main body is an inorganic particle.

  In another specific aspect of the conductive particle with insulating particles according to the present invention, the polymer compound is at least one reactive functional group selected from the group consisting of a (meth) acryloyl group, a glycidyl group, and a vinyl group. Has a group.

  A connection structure according to the present invention includes a first connection target member, a second connection target member, and a connection portion connecting the first and second connection target members, and the connection portion. Is formed of an anisotropic conductive material including conductive particles with insulating particles or the conductive particles with insulating particles and a binder resin, which are configured according to the present invention.

  According to a wide aspect of the present invention, a layer formed of a polymer compound using a polymer compound or a compound that becomes a polymer compound so as to cover at least a part of the surface of the insulating particle body. Forming the insulating particles, and attaching the insulating particles to the surface of the conductive particles having at least the surface of the conductive layer, and the insulating particles on the surface of the conductive particles are attached. There is provided a method for producing conductive particles with insulating particles, comprising a step of obtaining conductive particles with insulating particles to which the polymer compound is not attached to a portion other than the portion.

  According to another broad aspect of the present invention, a layer formed of a polymer compound using a polymer compound or a compound that becomes a polymer compound so as to cover at least a part of the surface of the insulating particle body. Forming the insulating particles, and attaching the insulating particles to the surface of the conductive particles having at least a conductive layer on the surface by a method other than the hybridization method, so that the insulating particles are hybridized. A method for producing conductive particles with insulating particles, comprising the step of obtaining conductive particles with insulating particles that are not attached by the above.

  The anisotropic conductive material according to the present invention is a conductive particle with insulating particles obtained by the method for producing conductive particles with insulating particles according to the present invention or conductive particles with insulating particles according to the present invention. And a binder resin.

  In the conductive particles with insulating particles according to the present invention, the insulating particles attached to the surface of the conductive particles cover the insulating particle main body and at least a part of the surface of the insulating particle main body. And having a layer formed of a polymer compound, the insulating particles can be prevented from being unintentionally detached from the surface of the conductive particles.

  In the method for producing conductive particles with insulating particles according to the present invention, a polymer compound or a compound that becomes a polymer compound is used in at least a part of the surface of the insulating particle main body to form the polymer compound. After the insulating layer is formed and the insulating particles are obtained, the insulating particles are adhered to the surface of the conductive particles, so that the insulating particles are difficult to be detached from the surface of the conductive particles. Can be obtained.

  Therefore, using the conductive particles with insulating particles according to the present invention or using the conductive particles with insulating particles obtained by the method for producing conductive particles with insulating particles according to the present invention, the gap between the electrodes is determined. Even if a plurality of conductive particles with insulating particles come into contact with each other, there are insulating particles between adjacent conductive particles, so the adjacent electrodes that should not be connected are electrically connected. It is hard to be done. For this reason, the conduction | electrical_connection reliability between electrodes can be improved.

FIG. 1 is a cross-sectional view showing conductive particles with insulating particles according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view showing conductive particles with insulating particles according to the second embodiment of the present invention. FIG. 3 is a front sectional view schematically showing a connection structure using the conductive particles with insulating particles shown in FIG. 1. FIG. 4 is a cross-sectional view showing a conventional conductive particle with insulating particles using a hybridization method.

  Hereinafter, the present invention will be clarified by describing specific embodiments and examples of the present invention with reference to the drawings.

(Conductive particle body with insulating particles)
FIG. 1 is a sectional view showing conductive particles with insulating particles according to the first embodiment of the present invention.

  A conductive particle 1 with insulating particles shown in FIG. 1 includes conductive particles 2 and a plurality of insulating particles 3 attached to the surface of the conductive particles 2.

  The insulating particles 3 include an insulating particle body 5 and a layer 6 that covers the surface of the insulating particle body 5 and is formed of a polymer compound. The insulating particles 3 are made of an insulating material.

  The layer 6 covers the entire surface of the insulating particle body 5. Therefore, the layer 6 is disposed between the conductive particles 2 and the insulating particle main body 5. The layer 6 may be present so as to cover at least a part of the surface of the insulating particle main body, and may not cover the entire surface of the insulating particle main body. The layer 6 is preferably disposed between the conductive particles and the insulating particle main body.

  The conductive particles 2 include base material particles 11 and a conductive layer 12 provided on the surface of the base material particles 11. The conductive layer 12 covers the surface of the base particle 11. The conductive particle 2 is a coated particle in which the surface of the base particle 11 is coated with the conductive layer 12. The conductive particles 2 have a conductive layer 12 on the surface.

  FIG. 2 is a sectional view showing conductive particles with insulating particles according to the second embodiment of the present invention.

  The conductive particles 21 with insulating particles shown in FIG. 2 include conductive particles 22 and a plurality of insulating particles 3 attached to the surface of the conductive particles 22.

  The conductive particles 22 have base material particles 11 and a conductive layer 31 provided on the surface of the base material particles 11. The conductive particles 22 have a plurality of core substances 32 on the surface of the substrate particles 11. The conductive layer 31 covers the base particle 11 and the core substance 32. By covering the core substance 32 with the conductive layer 31, the conductive particles 22 have a plurality of protrusions 33 on the surface. The surface of the conductive layer 31 is raised by the core substance 32, and a plurality of protrusions 33 are formed.

  The main features of the first to second embodiments are that the insulating particles 3 attached to the surfaces of the conductive particles 2 and 22 cover the insulating particle body 5 and the surface of the insulating particle body 5. And the layer 6 formed of a polymer compound, and the polymer compound is not attached to any part of the surface of the conductive particles other than the part to which the insulating particles are attached. Alternatively, the insulating particles are not attached by a hybridization method. Thereby, in the conductive particles 1 and 21 with the insulating particles, the insulating particles 3 are hardly detached from the surfaces of the conductive particles 2 and 22. For example, when the conductive particles 1 and 21 with insulating particles are added to the binder resin and kneaded, the insulating particles 3 are not easily detached from the surfaces of the conductive particles 2 and 22. For this reason, when the conductive particles 1 and 21 with insulating particles are used for the connection between the electrodes, the insulating particles 3 exist between the adjacent conductive particles 2 and 22, so that they should not be connected to each other. It is difficult to electrically connect the matching electrodes. Therefore, when the electrodes are connected using the conductive particles 1 and 21 with insulating particles, the conduction reliability can be improved.

  In the conductive particles with insulating particles according to the present invention, the residual ratio of the insulating particles is preferably 60 to 95%. The residual ratio of the insulating particles is more preferably 70% or more, and more preferably 90% or less. When the remaining ratio of the insulating particles is equal to or more than the above lower limit, the insulating particles are hardly detached from the surface of the conductive particles when the conductive particles with the insulating particles are added to the binder resin and kneaded. When the conductive particles with particles are connected between the electrodes, leakage hardly occurs between adjacent electrodes that should not be connected. When the residual ratio of the insulating particles is not more than the above upper limit, the continuity of the upper and lower electrodes to be connected can be sufficiently ensured.

  The “residual ratio of insulating particles” is obtained as follows.

  Before the following ultrasonic treatment, 100 conductive particles with insulating particles were observed by observation with a scanning electron microscope (SEM), and the coverage X1 (%) of the conductive particles in the conductive particles with insulating particles was observed. (Also referred to as adhesion rate X1 (%)) is obtained. The said coverage is an area of the part coat | covered with the insulating particle which occupies for the whole surface area of electroconductive particle.

  Next, 3 parts by weight of conductive particles with insulating particles are added to 100 parts by weight of ethanol to obtain a conductive particle-containing liquid with insulating particles. This conductive particle-containing liquid with insulating particles is subjected to ultrasonic treatment while being stirred for 5 minutes at 20 ° C. and 40 kHz with an ultrasonic cleaner. After the ultrasonic treatment, 100 conductive particles with insulating particles are observed by observation with an SEM, and the portion of the conductive particles with insulating particles covered by the insulating particles occupying the entire surface area of the conductive particles. The area coverage ratio X2 (%) (also referred to as adhesion rate X2 (%)) is obtained. The residual rate of the insulating particles is a value represented by the following formula (1) from the coverage X1 and the coverage X2.

  Residual rate of insulating particles (%) = (coverage ratio X2 after ultrasonic treatment / coverage ratio X1 before ultrasonic treatment) × 100 Formula (1)

  In order to appropriately expose the surface of the conductive particles, the coverage of the insulating particles is preferably 5% or more, more preferably 40% or more. The said coverage shows the area of the part coat | covered with the insulating particle which occupies for the whole surface area of electroconductive particle. When the coverage is equal to or higher than the lower limit, adjacent conductive particles are more difficult to contact. The coverage of the insulating particles is preferably 70% or less. When the coverage of the insulating particles is 70% or less, the insulating particles can be sufficiently eliminated without applying heat and pressure more than necessary when the electrodes are connected.

  The conductive particles with insulating particles have a layer formed of a polymer compound using a polymer compound or a compound that becomes a polymer compound so as to cover at least a part of the surface of the insulating particle body. A step of forming and obtaining insulating particles, and a portion where the insulating particles are attached to the surface of the conductive particles having at least a conductive layer on the surface, and the insulating particles are attached to the surface of the conductive particles It is preferable to obtain it through a step of obtaining conductive particles with insulating particles in which the polymer compound is not attached to other portions. Further, the conductive particles with insulating particles are formed of a high molecular compound using a high molecular compound or a compound that becomes a high molecular compound so as to cover at least a part of the surface of the insulating particle main body. Forming a layer to obtain insulating particles, and attaching the insulating particles to the surface of the conductive particles having at least a conductive layer on the surface by a method other than the hybridization method, so that the insulating particles are hybridized. It is preferably obtained through a step of obtaining conductive particles with insulating particles that are not attached by the method.

  Hereinafter, details of the conductive particles 2 and 22 and details of the insulating particles 3 will be described.

[Conductive particles]
Conductive particles with insulating particles can be obtained by attaching the insulating particles to the surface of conductive particles having at least a conductive layer on the surface.

  The conductive particles only need to have a conductive layer on at least the surface. The conductive particles may be conductive particles having base material particles and a conductive layer provided on the surface of the base material particles, or may be metal particles whose entirety is a conductive layer. Among these, from the viewpoint of reducing costs and increasing the flexibility of the conductive particles to increase the conduction reliability between the electrodes, the base particles and the conductive material provided on the surface of the base particles are used. Conductive particles having a layer are preferred.

  Examples of the substrate particles include resin particles, inorganic particles, organic-inorganic hybrid particles, and metal particles.

  The substrate particles are preferably resin particles formed of a resin. When connecting the electrodes using the conductive particles with insulating particles, the conductive particles with insulating particles are compressed by placing the conductive particles with insulating particles between the electrodes and then pressing them. When the substrate particles are resin particles, the conductive particles are easily deformed during the above-described pressure bonding, and the contact area between the conductive particles and the electrode can be increased. For this reason, the conduction | electrical_connection reliability between electrodes can be improved.

  Examples of the resin for forming the resin particles include polyolefin resin, acrylic resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, and polyphenylene. Examples thereof include oxides, polyacetals, polyimides, polyamideimides, polyetheretherketones, and polyethersulfones. Since the hardness of the base particles can be easily controlled within a suitable range, the resin for forming the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferably a coalescence.

  Examples of the inorganic substance for forming the inorganic particles include silica and carbon black. Examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

  When the substrate particles are metal particles, examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium.

  The metal for forming the conductive layer is not particularly limited. Furthermore, when the conductive particles are metal particles that are conductive layers as a whole, the metal for forming the metal particles is not particularly limited. Examples of the metal include gold, silver, copper, palladium, platinum, palladium, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, and silicon. And alloys thereof. Examples of the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes can be made still lower, an alloy containing tin and tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is more preferable.

  Note that hydroxyl groups often exist on the surface of the conductive layer due to oxidation. In general, hydroxyl groups are present on the surface of a conductive layer formed of nickel by oxidation. Such a conductive layer having a hydroxyl group is easily chemically bonded to the insulating particles, for example, chemically bonded to the insulating particles having a hydroxyl group.

  The conductive layer is formed of one layer. The conductive layer may be formed of a plurality of layers. That is, the conductive layer may have a stacked structure of two or more layers. When the conductive layer is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and is a gold layer. Is more preferable. When the outermost layer is these preferred conductive layers, the connection resistance between the electrodes can be further reduced. Further, when the outermost layer is a gold layer, the corrosion resistance can be further enhanced.

  The method for forming the conductive layer on the surface of the substrate particles is not particularly limited. As a method for forming the conductive layer, for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating the surface of base particles with metal powder or a paste containing metal powder and a binder Etc. Especially, since formation of a conductive layer is simple, the method by electroless plating is preferable. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.

  The average particle size of the conductive particles is preferably in the range of 0.5 to 100 μm. The average particle diameter of the conductive particles is more preferably 1 μm or more, and more preferably 20 μm or less. When the average particle diameter of the conductive particles is not less than the above lower limit and not more than the upper limit, the contact area between the conductive particles and the electrodes is sufficiently increased when the conductive particles with insulating particles are connected between the electrodes. In addition, it is difficult to form aggregated conductive particles when the conductive layer is formed. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.

  The “average particle size” of the conductive particles indicates a number average particle size. The average particle diameter of the conductive particles can be obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.

  The conductive layer preferably has a thickness in the range of 0.005 to 1 μm. The thickness of the conductive layer is more preferably 0.01 μm or more, and more preferably 0.3 μm or less. When the thickness of the conductive layer is not less than the above lower limit and not more than the upper limit, sufficient conductivity can be obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed when connecting between the electrodes. Can be made.

  When the conductive layer is formed of a plurality of layers, the thickness of the outermost conductive layer is within the range of 0.001 to 0.5 μm, particularly when the outermost layer is a gold layer. It is preferable that A more preferable lower limit of the thickness of the outermost conductive layer is 0.01 μm, and a more preferable upper limit is 0.1 μm. When the thickness of the outermost conductive layer is not less than the above lower limit and not more than the upper limit, the outermost conductive layer can be uniformly coated, the corrosion resistance can be sufficiently increased, and the connection resistance between the electrodes is sufficiently low. can do. Further, the thinner the gold layer when the outermost layer is a gold layer, the lower the cost.

  The thickness of the conductive layer can be measured, for example, by observing the cross section of the conductive particles or the conductive particles with insulating particles using a transmission electron microscope (TEM).

  The conductive particles preferably have protrusions on the surface of the conductive layer, and the protrusions are preferably plural. An oxide film is often formed on the surface of the electrode connected by the conductive particles with insulating particles. When the conductive particles with insulating particles having protrusions on the surface of the conductive layer are used, the oxide film can be effectively eliminated by the protrusions by disposing the conductive particles between the electrodes and pressing them. For this reason, an electrode and a conductive layer can be contacted still more reliably and the connection resistance between electrodes can be made low. Furthermore, when the electrodes are connected, the insulating particles between the conductive particles and the electrodes can be effectively eliminated by the protrusions of the conductive particles. For this reason, the conduction | electrical_connection reliability between electrodes can be improved.

  As a method of forming protrusions on the surface of the conductive particles, a method of forming a conductive layer by electroless plating after attaching a core substance to the surface of the base particles, and by electroless plating on the surface of the base particles Examples of the method include forming a conductive layer, then attaching a core substance, and further forming a conductive layer by electroless plating.

  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, and 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. Especially, since the quantity of the core substance to adhere is easy to control, the method of making a core substance accumulate and adhere on the surface of the base particle in a dispersion liquid is preferable.

  Examples of the conductive material constituting the core material include conductive non-metals such as metals, metal oxides, and graphite, and conductive polymers. Examples of the conductive polymer include polyacetylene. Among them, metal is preferable because conductivity can be increased.

  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 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 conductive layer.

  The shape of the core material is not particularly limited. The shape of the core substance is preferably a lump. Examples of the core substance include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.

[Insulating particles]
The insulating particles are particles having insulating properties. Insulating particles are smaller than conductive particles. When the electrodes are connected using conductive particles with insulating particles, the insulating particles can prevent a short circuit between adjacent electrodes. Specifically, when the conductive particles with a plurality of insulating particles are in contact with each other, there are insulating particles between the conductive particles in the conductive particles with a plurality of insulating particles. Short circuit between the electrodes adjacent in the lateral direction can be prevented. Note that the insulating particles between the conductive layer and the electrode can be easily excluded by pressurizing the conductive particles with insulating particles with the two electrodes when connecting the electrodes. In the case where protrusions are provided on the surface of the conductive particles, the insulating particles between the conductive layer and the electrode can be more easily eliminated. Furthermore, since the protruding portion facilitates contact with the electrode, connection reliability is improved.

  Examples of the material constituting the insulating particles include an insulating resin and an insulating inorganic substance. As said insulating resin, the said resin quoted as resin for forming the resin particle which can be used as a base particle is mentioned. As said insulating inorganic substance, the said inorganic substance quoted as an inorganic substance for forming the inorganic particle which can be used as a base particle is mentioned.

  Specific examples of the insulating resin that is the material of the insulating particles include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked thermoplastic resins, heat Examples thereof include curable resins and water-soluble resins.

  Examples of the polyolefins include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer. Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate. Examples of the block polymer include polystyrene, styrene-acrylic acid ester copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, and hydrogenated products thereof. Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers. As said thermosetting resin, an epoxy resin, a phenol resin, a melamine resin, etc. are mentioned. 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.

  From the viewpoint of further increasing the detachability of the insulating particles during thermocompression bonding, the insulating particle body is preferably inorganic particles, and is preferably silica particles. Inorganic particles are relatively hard, especially silica particles are relatively hard. When conductive particles with insulating particles using such hard insulating particles as insulating particles are added to a binder resin and kneaded, the insulating particles are hard, so that the insulating particles are removed from the surface of the conductive particles. There is a tendency to detach easily.

  In contrast, when the surface of the inorganic particles is covered with a layer formed of a polymer compound as in the present invention, the insulating particles are further inorganic particles even if the insulating particles are hard. However, it is difficult for the insulating particles to be detached from the surface of the conductive particles during the kneading.

  The layer formed of the polymer compound serves as a flexible layer, for example.

  The polymer compound in the layer formed of the polymer compound or the compound that becomes the polymer compound by polymerization or the like is preferably a compound having a polymerizable reactive functional group. The polymerizable reactive functional group is preferably an unsaturated double bond. Examples of the polymer compound include a compound having a (meth) acryloyl group, a compound having an epoxy group, and a compound having a vinyl group. From the viewpoint of suppressing detachment of the insulating particles from the surface of the conductive particles when dispersing the conductive particles with insulating particles, the polymer compound or the compound to be the polymer compound is (meth) It preferably has at least one reactive functional group selected from the group consisting of an acryloyl group, a glycidyl group and a vinyl group. Among these, from the viewpoint of further suppressing the detachment of the insulating particles, the polymer compound or the compound to be the polymer compound preferably has a (meth) acryloyl group.

  Specific examples of the compound having the (meth) acryloyl group include methacrylic acid and hydroxyethyl acrylate.

  Specific examples of the epoxy compound include bisphenol A type epoxy resin and resorcinol glycidyl ether.

  Specific examples of the compound having a vinyl group include styrene and vinyl acetate.

  The polymer compound preferably has a weight average molecular weight of 1000 or more. The weight average molecular weight indicates a value in terms of polystyrene measured by gel permeation chromatography (GPC).

  The method for forming the layer formed of the polymer compound on the surface of the insulating particles is not particularly limited. Using a polymer compound or a compound that becomes a polymer compound so as to cover at least a part of the surface of the insulating particle main body, a layer formed of the polymer compound is formed to obtain insulating particles. preferable. As an example of a method for forming a layer formed of the polymer compound, a compound having a reactive double bond and a hydroxyl group is formed on an insulating particle body having a reactive functional group such as a vinyl group on the surface. And a method of polymerizing on the surface. However, methods other than this forming method may be used.

  The following manufacturing conditions are mentioned as an example of the specific manufacturing conditions of the layer formed with the said high molecular compound.

  First, in 100 to 500 parts by weight of a solvent such as water, 1 to 3 parts by weight of an insulating particle body having a reactive functional group on the surface, and 0.1 to 1 part by weight of a compound having a reactive double bond and a hydroxyl group , 0.01 to 1 part by weight of a crosslinking agent, 0.1 to 3 parts by weight of a dispersant and 0.1 to 3 parts by weight of a thermal polymerization initiator are added. Next, while stirring with a three-one motor, the temperature is raised to a temperature higher than the reaction temperature of the thermal polymerization initiator in an oil bath, polymerization is started, and the state is maintained for 5 hours or longer to react. Thereafter, unreacted compounds are removed using a centrifuge to obtain insulating particles in which the surface of the insulating particle main body is covered with the layer.

  When there are hydroxyl groups on the surface of the insulating particles and the surface of the conductive particles, the adhesion force between the insulating particles and the conductive particles is appropriately increased by the dehydration reaction.

  Examples of the compound having a hydroxyl group for introducing a hydroxyl group include a P—OH group-containing compound and a Si—OH group-containing compound.

  Specific examples of the P-OH group-containing compound include acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, and acid phosphooxypolyoxypropylene glycol monomethacrylate. As for the said P-OH group containing compound, only 1 type may be used and 2 or more types may be used together.

  Specific examples of the Si-OH group-containing compound include vinyltrihydroxysilane and 3-methacryloxypropyltrihydroxysilane. As for the said Si-OH group containing compound, only 1 type may be used and 2 or more types may be used together.

  For example, insulating particles having a hydroxyl group on the surface can be obtained by a treatment using a silane coupling agent. Examples of the silane coupling agent include hydroxytrimethoxysilane.

  The particle diameter of the insulating particles can be appropriately selected depending on the particle diameter of the conductive particles, the use of the conductive particles with insulating particles, and the like. The average particle size of the insulating particles is preferably in the range of 0.005 to 1 μm. The average particle diameter of the insulating particles is more preferably 0.01 μm or more, and more preferably 0.5 μm or less. When the average particle diameter of the insulating particles is not less than the above lower limit, the conductive particles in the plurality of conductive particles with insulating particles are difficult to contact when the conductive particles with insulating particles are dispersed in the binder resin. Become. When the average particle diameter of the insulating particles is not more than the above upper limit, it is not necessary to make the pressure too high in order to eliminate the insulating particles between the electrodes and the conductive particles when connecting the electrodes, There is no need to heat to high temperatures.

  The “average particle diameter” of the insulating particles indicates a number average particle diameter. The average particle size of the insulating particles is determined using a particle size distribution measuring device or the like.

  The average particle size of the insulating particles is preferably 1/5 or less of the average particle size of the conductive particles. The average particle size of the insulating particles is preferably 1/1000 or more of the average particle size of the conductive particles. When the average particle diameter of the insulating particles is 1/5 or less of the average particle diameter of the conductive particles, for example, when manufacturing the conductive particles with insulating particles, the insulating particles are further separated on the surface of the conductive particles. It can be attached efficiently.

  Two or more insulating particles having different particle diameters may be used. In this case, since small insulating particles can exist between the large insulating particles on the surface of the conductive particles, the exposed area of the conductive particles can be reduced. Therefore, even if a plurality of conductive particles with insulating particles are in contact with each other, adjacent conductive particles are difficult to contact, and thus a short circuit between adjacent electrodes can be suppressed. The average particle size of the small insulating particles is preferably 1/2 or less of the average particle size of the large insulating particles. The number of small insulating particles is preferably ¼ or less of the number of large insulating particles.

  The layer formed of the polymer compound preferably has higher flexibility than the insulating particle body. In general, a layer formed of a polymer compound formed of an organic compound has higher flexibility than inorganic particles. The flexibility between the layer and the insulating particle body can be evaluated, for example, by measuring the recovery rate.

  The recovery rate can be calculated, for example, by calculating the ratio of the amount of change in particle size when added to the amount of change in particle size when a constant load is applied to the insulating particles.

  For example, insulating particles whose surfaces are coated with a layer formed of a polymer compound are subjected to 1N compression using a micro-compression tester (manufactured by Shimadzu Corporation), and then added to the particles. The compression recovery rate can be measured by measuring the deformation.

In the measurement, the insulating particles were put into a 1 cm ³ (inner diameter 1 cm × width 1 cm × height 1 cm) stainless steel cup so as to be closely packed, and then 0.90 cm ² (length 0.95 cm × width 0.3 mm). A 95 cm) stainless steel lid may be installed so as to be movable, a compression test may be performed from the top of the lid, and the recovery rate may be measured from the range of movement of the lid.

(Conductive particles with insulating particles)
Examples of the method for attaching the insulating particles to the surfaces of the conductive particles and the conductive layer include chemical methods and physical or mechanical methods. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method. Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spraying, dipping, and vacuum deposition. However, since the hybridization method tends to cause the detachment of the insulating particles, the method of attaching the insulating particles to the surfaces of the conductive particles and the conductive layer is a method other than the hybridization method. Is preferred. Among these, a method of attaching the insulating particles to the surface of the conductive layer through a chemical bond is preferable because the insulating particles are not easily detached.

  In the conductive particles with insulating particles according to the present invention, the insulating particles are preferably not attached by a hybridization method.

  As shown in FIG. 4, in the conventional conductive particles 101 with insulating particles using the hybridization method, the portions 102 b other than the portions 102 a on the surface of the conductive particles 102 are attached to the portions 102 b. Also, the polymer compound 104 adheres. This is because in the hybridization method, a compressive shear force is applied, the insulating particles are repeatedly attached and detached, and the insulating particles are gradually attached. The layer formed of the polymer compound of the insulating particles is peeled off by the compressive shearing force, and the peeled polymer compound is attached to a portion other than the portion where the insulating particles are attached on the surface of the conductive particles. The polymer compound adhering to the portion other than the portion to which the insulating particles adhere on the surface of the conductive particles increases the volume resistivity of the conductive particles or decreases the connection resistance between the electrodes.

  The following method is mentioned as an example of the method of attaching insulating particle | grains to the surface of the said electroconductive particle and the said conductive layer.

  First, the conductive particles are put in 3 L of a solvent such as water, and the insulating particles are gradually added while stirring. After sufficiently stirring, the conductive particles with insulating particles are separated and dried by a vacuum dryer or the like to obtain conductive particles with insulating particles.

  The conductive layer preferably has a reactive functional group capable of reacting with insulating particles on the surface. The insulating particles preferably have a reactive functional group capable of reacting with the conductive layer on the surface. These reactive functional groups make it difficult for the insulating particles to be unintentionally detached from the surface of the conductive particles.

  As the reactive functional group, an appropriate group is selected in consideration of reactivity. Examples of the reactive functional group include a hydroxyl group, a vinyl group, and an amino group. Since the reactivity is excellent, the reactive functional group is preferably a hydroxyl group. The conductive particles preferably have a hydroxyl group on the surface. The insulating particles preferably have a hydroxyl group on the surface.

(Anisotropic conductive material)
The anisotropic conductive material according to the present invention includes conductive particles with insulating particles according to the present invention, or conductive particles with insulating particles obtained by the method for producing conductive particles with insulating particles according to the present invention, and a binder. Resin.

  When the conductive particles with insulating particles are used, the insulating particles are unlikely to be detached from the surface of the conductive particles when the conductive particles with insulating particles are dispersed in the binder resin.

  The binder resin is not particularly limited. In general, an insulating resin is used as the binder resin. Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for the said 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 resins, ethylene-vinyl acetate copolymers, and polyamide resins. Examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin. The curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. 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, and a styrene-isoprene. -Hydrogenated product of a styrene block copolymer. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

  In addition to the conductive particles with insulating particles and the binder resin, the anisotropic conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, and an antioxidant. In addition, various additives such as a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.

  The method for dispersing the conductive particles with insulating particles in the binder resin is not particularly limited, and a conventionally known dispersion method can be used. Examples of a method for dispersing conductive particles with insulating particles in a binder resin include, for example, a method in which conductive particles with insulating particles are added to a binder resin and then kneaded and dispersed with a planetary mixer or the like. Conductive particles with particles are uniformly dispersed in water or an organic solvent using a homogenizer or the like, then added to the binder resin, kneaded and dispersed with a planetary mixer, etc., and the binder resin is water or organic Examples include a method of adding conductive particles with insulating particles after diluting with a solvent or the like, and kneading and dispersing with a planetary mixer or the like.

  The anisotropic conductive material according to the present invention can be used as an anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, anisotropic conductive film, or anisotropic conductive sheet. When the anisotropic conductive material according to the present invention is used as a film-like adhesive such as an anisotropic conductive film or an anisotropic conductive sheet, the film-like adhesive containing the conductive particles, A film-like adhesive that does not contain conductive particles may be laminated.

  The anisotropic conductive material according to the present invention is preferably an anisotropic conductive paste. An anisotropic conductive paste is excellent in handleability and circuit fillability. When obtaining an anisotropic conductive paste, a relatively large force is imparted to the conductive particles with insulating particles, but by using the conductive particles with insulating particles of the present invention, insulation from the surface of the conductive particles is achieved. It is possible to suppress the separation of the particles.

  In 100% by weight of the anisotropic conductive material, the content of the binder resin is preferably in the range of 10 to 99.99% by weight. The content of the binder resin is more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, and more preferably 99.9% by weight or more. When the content of the binder resin is not less than the above lower limit and not more than the upper limit, the conductive particles with insulating particles can be efficiently arranged between the electrodes, and the conduction reliability of the connection target member connected by the anisotropic conductive material is improved. It can be further increased.

  In 100% by weight of the anisotropic conductive material, the content of the conductive particles with insulating particles is preferably in the range of 0.01 to 20% by weight. The content of the conductive particles with the upper insulating particles is more preferably 0.1% by weight or more, and more preferably 15% by weight or less. When the content of the conductive particles with insulating particles is not less than the above lower limit and not more than the upper limit, the conduction reliability between the electrodes can be further enhanced.

(Connection structure)
By using the conductive particles with insulating particles of the present invention or the anisotropic conductive material containing the conductive particles with insulating particles and a binder resin, a connection structure can be obtained by connecting the connection target members. it can. Furthermore, by using the conductive particles with insulating particles obtained by the method for producing conductive particles with insulating particles of the present invention or an anisotropic conductive material containing the conductive particles with insulating particles and a binder resin, A connection structure can be obtained by connecting the connection target members.

  The connection structure includes a first connection target member, a second connection target member, and a connection portion that electrically connects the first and second connection target members. It is preferably a connection structure formed of an anisotropic conductive material containing conductive particles with insulating particles or conductive particles with insulating particles and a binder resin. When conductive particles with insulating particles are used, the connection portion itself is conductive particles. That is, the first and second connection target members are connected by the conductive particles.

  FIG. 3 is a cross-sectional view schematically showing a connection structure using the conductive particles 1 with insulating particles shown in FIG.

  A connection structure 51 shown in FIG. 3 includes a first connection target member 52, a second connection target member 53, and a connection portion 54 connecting the first and second connection target members 52 and 53. Prepare. The connection part 54 is formed of an anisotropic conductive material including the conductive particles 1 with insulating particles and a binder resin. In FIG. 3, the conductive particles 1 with insulating particles are schematically shown for convenience of illustration. Instead of the conductive particles 1 with insulating particles, conductive particles 21 with insulating particles may be used.

  A plurality of electrodes 52 b are provided on the upper surface 52 a of the first connection target member 52. A plurality of electrodes 53 b are provided on the lower surface 53 a of the second connection target member 53. The electrode 52b and the electrode 53b are electrically connected by one or more conductive particles 1 with insulating particles. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1 with insulating particles.

  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 disposed between a first connection target member and a second connection target member to obtain a laminate, and then the laminate is heated and The method of pressurizing is mentioned.

The pressure of the said pressurization is about 9.8-10 < ⁴ > -4.9 * 10 < ⁶ > Pa. The temperature of the said heating is about 120-220 degreeC.

  When the laminate is heated and pressed, the insulating particles 3 existing between the conductive particles 2 and the electrodes 52b and 53b can be eliminated. For example, during the heating and pressurization, the insulating particles 3 existing between the conductive particles 2 and the electrodes 52b and 53b are melted or deformed, so that the surface of the conductive particles 2 Is partially exposed. Note that a large force is applied during the heating and pressurization, so that some of the insulating particles 3 are peeled off from the surface of the conductive particles 2 and the surface of the conductive particles 2 is partially exposed. Sometimes. The portion where the surface of the conductive particle 2 is exposed contacts the electrodes 52b and 53b, whereby the electrodes 52b and 53b can be electrically connected via the conductive particle 2.

  Specific examples of the connection target member include electronic components such as semiconductor chips, capacitors, and diodes, and circuit boards such as printed boards, flexible printed boards, and glass boards.

  Examples of the electrode provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode. When the connection object member is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. In addition, when the said electrode is an aluminum electrode, the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated | stacked on the surface of the metal oxide layer may be sufficient. Examples of the metal oxide include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.

  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.

Example 1
Conductive particles (average particle diameter: 3.01 μm, conductive layer thickness: 0.2 μm) having a nickel plating layer (conductive layer) formed on the surface of divinylbenzene resin particles were prepared.

  Moreover, the surface of the silica particle (average particle diameter 200nm) produced using the sol-gel method was coat | covered with vinyltriethoxysilane, and the insulating particle which has a vinyl group on the surface was obtained as an insulating particle main body.

  In 200 mL of water, 1 part by weight of the insulating particle main body, 0.22 parts by weight of methacrylic acid as a polymer compound, and 0.05 part by weight of ethylene glycol dimethacrylate as a compound as a polymer compound And 0.5 parts by weight of an initiator (“V-50” manufactured by Wako Pure Chemical Industries, Ltd.) were heated to 70 ° C. with sufficient stirring with a three-one motor, held at 70 ° C. for 6 hours, and the above monomer Was polymerized.

  Then, it cooled, solid-liquid separation was performed twice with the centrifuge, the excess monomer was removed by washing | cleaning, and the insulating particle by which the whole surface was coat | covered with the high molecular compound was obtained. Next, the obtained insulating particles were dispersed in 30 mL of pure water to obtain a dispersion of insulating particles.

  A 1 L separable flask was charged with 250 mL of pure water, 50 mL of ethanol, and 15 parts by weight of the conductive particles, and stirred sufficiently to obtain a liquid containing conductive particles. To the liquid containing the conductive particles, the dispersion liquid of the insulating particles was dropped over 10 minutes while applying ultrasonic waves, and then heated to 40 ° C. and stirred for 1 hour. Then, it filtered and it was made to dry at 100 degreeC with a vacuum dryer for 8 hours, and the electroconductive particle with an insulating particle was obtained.

(Example 2)
When obtaining insulating particles whose entire surface is coated with a polymer compound, the compound that becomes the polymer compound was changed to 0.33 parts by weight of methacrylic acid and 0.05 parts by weight of divinylbenzene. In the same manner as in Example 1, conductive particles with insulating particles were obtained.

(Example 3)
The surface of the silica particles was coated with methacryloxypropyltriethoxysilane to obtain insulating particles having methacryloyl groups on the surface as the insulating particle main body, and the entire surface was made of a polymer compound using the insulating particle main body. Example 1 except that when the coated insulating particles were obtained, the polymer compound was changed to 0.28 parts by weight of vinyl acetate and 0.05 parts by weight of N, N-methylenebisacrylamide. In the same manner, conductive particles with insulating particles were obtained.

(Example 4)
Conductivity in which nickel powder (100 nm) is attached as a core material to the surface of divinylbenzene resin particles, and a nickel plating layer (conductive layer) is formed on the surface of divinylbenzene particles to which nickel powder is attached Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that particles (average particle size: 3.03 μm, conductive layer thickness: 0.21 μm) were used.

(Comparative Example 1)
Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the surface of the insulating particle main body was not coated with the polymer compound.

  That is, when the insulating particles are attached to the surface of the conductive particles, the insulating particles (not coated with the polymer compound) having the vinyl group on the surface are used as pure water as a dispersion of the insulating particles. A dispersion liquid dispersed in 30 mL was used.

(Comparative Example 2)
Using the physical / mechanical hybridization method, the insulating particles produced in Example 1 were attached to the conductive particles prepared in Example 1 to obtain conductive particles with insulating particles.

(Evaluation)
(1) Coverage rate of conductive particles with insulating particles and residual rate of insulating particles Before sonication, 100 conductive particles with insulating particles of Examples and Comparative Examples were observed by observation with an SEM. . The coverage X1, which is the area of the portion covered with the insulating particles in the entire surface area of the conductive particles in the conductive particles with insulating particles, was determined.

  Next, 3 parts by weight of conductive particles with insulating particles was added to 100 parts by weight of ethanol to obtain a conductive particle-containing liquid with insulating particles. The conductive particle-containing liquid with insulating particles was subjected to ultrasonic treatment while being stirred for 5 minutes at 20 ° C. and 40 kHz with an ultrasonic cleaner. After the ultrasonic treatment, 100 conductive particles with insulating particles are observed by observation with an SEM, and the portion of the conductive particles with insulating particles covered by the insulating particles occupying the entire surface area of the conductive particles. The area coverage X2 was determined. The remaining rate of the insulating particles was obtained from the following formula (1) from the coverage X1 and the coverage X2.

  Residual rate of insulating particles (%) = (X2 / X1) × 100 Formula (1)

(2) Preparation of connection structure The conductive particles with insulating particles of Examples and Comparative Examples were added to and dispersed in “Struct Bond XN-5A” manufactured by Mitsui Chemicals so that the content would be 10% by weight. An anisotropic conductive paste was obtained.

  A transparent glass substrate having an ITO electrode pattern with an L / S of 30 μm / 30 μm formed on the upper surface was prepared. Further, a semiconductor chip was prepared in which a copper electrode pattern having L / S of 30 μm / 30 μm was formed on the lower surface.

  On the transparent glass substrate, the obtained anisotropic conductive paste was applied to a thickness of 30 μm to form an anisotropic conductive paste layer. Next, the semiconductor chip was stacked on the anisotropic conductive paste layer so that the electrodes face each other. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 185 ° C., a pressure heating head is placed on the upper surface of the semiconductor chip and a pressure of 1 MPa is applied to form the anisotropic conductive paste layer. Completely cured at 185 ° C. to obtain a connection structure.

(3) Conductivity evaluation 1 (between upper and lower electrodes)
The connection resistance between the upper and lower electrodes of the obtained connection structure was measured by a four-terminal method. The average value of the two connection resistances was calculated. Note that the connection resistance can be obtained by measuring the voltage when a constant current is passed from the relationship of voltage = current × resistance. The results are shown in Table 1 below, where “◯” indicates that the average value of the connection resistance is 2.0Ω or less, and “X” indicates that the average value of the connection resistance exceeds 2Ω.

(4) Insulation evaluation (between adjacent electrodes in the horizontal direction)
In the obtained connection structure, the presence or absence of leakage between adjacent electrodes was evaluated by measuring resistance with a tester. When the resistance exceeds 500 MΩ, it is determined that there is no leakage, and the result is “◯”. When the resistance is 500 MΩ or less, it is determined that there is leakage, and the result is “X”.

(5) Conductivity evaluation 2 (volume resistance)
Using a powder resistance measurement system (manufactured by Mitsubishi Chemical Analytech), the volume resistivity of the obtained conductive particles with insulating particles was measured. The case where the volume resistivity is 0.0015 Ω · cm or less is “◯”, and the case where the volume resistivity exceeds 0.0015 Ω · cm is “x”.

  In addition, in the insulating particles obtained in Examples 1 to 3, the layer formed of the polymer compound has higher flexibility than the silica particles by measuring the compression recovery rate of the insulating particles. It was confirmed.

  Moreover, in the conductive particles with insulating particles of Examples 1 to 4, it was confirmed that the polymer compound was not attached to a portion other than the portion to which the insulating particles were attached on the surface of the conductive particles. . On the other hand, in the conductive particles with insulating particles of Comparative Example 2, the polymer compound was attached to a portion other than the portion to which the insulating particles were attached on the surface of the conductive particles. For this reason, in the electroconductive particle with an insulating particle of the comparative example 2, the evaluation result of electroconductivity evaluation (volume resistance) was bad.

DESCRIPTION OF SYMBOLS 1 ... Conductive particle with insulating particle 2 ... Conductive particle 3 ... Insulating particle 5 ... Insulating particle main body 6 ... Layer 11 ... Base particle 12 ... Conductive layer 21 ... Conductive particle with insulating particle 22 ... Conductive Particle 31 ... Conductive layer 32 ... Core material 33 ... Protrusion 51 ... Connection structure 52 ... First connection object member 52a ... Upper surface 52b ... Electrode 53 ... Second connection object member 53a ... Lower surface 53b ... Electrode 54 ... Connection part

Claims (7)

Conductive particles having at least a conductive layer on the surface;
Insulating particles attached to the surface of the conductive particles,
The insulating particles have an insulating particle main body, and a layer that covers at least a part of the surface of the insulating particle main body and is formed of a polymer compound;
The insulating particle body is inorganic particles,
The polymer compound has at least one reactive functional group selected from the group consisting of a (meth) acryloyl group, a glycidyl group and a vinyl group;
Conductive particles with insulating particles, wherein the polymer compound is not attached to a portion other than the portion to which the insulating particles are attached on the surface of the conductive particles. Conductive particles having at least a conductive layer on the surface;
Insulating particles attached to the surface of the conductive particles,
The insulating particles have an insulating particle main body, and a layer that covers at least a part of the surface of the insulating particle main body and is formed of a polymer compound;
The insulating particle body is inorganic particles,
The polymer compound has at least one reactive functional group selected from the group consisting of a (meth) acryloyl group, a glycidyl group and a vinyl group;
Conductive particles with insulating particles, wherein the insulating particles are not attached by a hybridization method. An anisotropic conductive material comprising the conductive particles with insulating particles according to claim 1 or 2 and a binder resin. A first connection target member, a second connection target member, and a connection portion connecting the first and second connection target members;
The connection structure in which the said connection part is formed with the anisotropic conductive material containing the electroconductive particle with an insulating particle of Claim 1 or 2 , or this electroconductive particle with an insulating particle, and binder resin. Forming a layer formed of a polymer compound by using a polymer compound or a compound to be a polymer compound so as to cover at least a part of the surface of the insulating particle main body, and obtaining insulating particles; ,
The insulating particles are attached to the surface of the conductive particles having at least a conductive layer on the surface, and the polymer compound is attached to a portion other than the portion where the insulating particles are attached to the surface of the conductive particles. A step of obtaining conductive particles with insulating particles that are not ,
The insulating particle body is inorganic particles,
The polymer compound, (meth) acryloyl group, that having a least one reactive functional group selected from the group consisting of glycidyl group and a vinyl group, the manufacturing method of the insulating particles with the conductive particles. Forming a layer formed of a polymer compound by using a polymer compound or a compound to be a polymer compound so as to cover at least a part of the surface of the insulating particle main body, and obtaining insulating particles; ,
Conductive particles with insulating particles in which the insulating particles are attached to the surface of the conductive particles having at least a conductive layer on the surface by a method other than the hybridization method, and the insulating particles are not attached by the hybridization method. and a step of obtaining a
The insulating particle body is inorganic particles,
The polymer compound, (meth) acryloyl group, that having a least one reactive functional group selected from the group consisting of glycidyl group and a vinyl group, the manufacturing method of the insulating particles with the conductive particles. And insulating particles with conductive particles obtained by the production method of the insulating particles with conductive particle according to claim 5 or 6, and a binder resin, the anisotropic conductive material.

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